Chemical amplification, positive resist compositions

ABSTRACT

A chemical amplification, positive resist composition is provided comprising (A) a photoacid generator and (B) a resin which changes its solubility in an alkali developer under the action of acid and has substituents of the formula: Ph—(CH 2 ) n OCH(CH 2 CH 3 )— wherein Ph is phenyl and n=1 or 2. The composition has many advantages including improved focal latitude, improved resolution, minimized line width variation or shape degradation even on long-term PED, minimized defect left after coating, development and stripping, and improved pattern profile after development and is suited for microfabrication by any lithography, especially deep UV lithography.

This invention relates to chemical amplification, positive resistcompositions which are sensitive to such radiation as UV, deep UV,electron beams, x-rays, excimer laser beams, γ-rays, and synchrotronradiation and suitable for the microfabrication of integrated circuits.

BACKGROUND OF THE INVENTION

While a number of efforts are currently being made to achieve a finerpattern rule in the drive for higher integration and operating speeds inLSI devices, deep-ultraviolet lithography is thought to hold particularpromise as the next generation in microfabrication technology. Deep UVlithography enables micropatterning to a feature size of 0.3 or 0.4 μm.One technology that has attracted a good deal of attention recentlyutilizes as the deep UV light source a high-intensity KrF excimer laser,especially an ArF excimer laser featuring a shorter wavelength. There isa desire to have a resist material capable of micropatterning to asmaller feature size.

In this regard, the recently developed, acid-catalyzed, chemicalamplification type positive resist materials (see JP-B 2-27660 and JP-A63-27829) are expected to comply with the deep UV lithography because oftheir many advantages including high sensitivity, resolution and dryetching resistance.

On use of the chemical amplification type resist compositions,especially chemical amplification type, positive working resistcompositions, a resist film is formed by dissolving a resin having acidlabile groups as a binder and a compound capable of generating an acidupon exposure to radiation (to be referred to as photoacid generator) ina solvent, applying the resist solution onto a substrate (inclusive of astepped substrate) by a variety of methods, and evaporating off thesolvent optionally by heating. The resist film is then exposed toradiation, for example, deep UV through a mask of a predeterminedpattern. This is optionally followed by post-exposure baking (PEB) forpromoting acid-catalyzed reaction. The exposed resist film is developedwith an aqueous alkaline developer for removing the exposed area of theresist film, obtaining a positive pattern profile. The pattern profileof resist is then transferred to the substrate by dry or wet etching.Since the stepped substrate and the aligner used in device fabricationhave more or less errors, there is a desire to have a resist materialcapable of forming an accurate pattern even when the focal point issomewhat offset, i.e., having a wide depth of focus.

Several acid labile group-substituted resins are known suitable for usein chemically amplified positive resist compositions. Included areresins protected with t-butyl ester groups or t-butoxycarbonyl groups(JP-B 2-27660 referred to above), resins protected with 1-ethoxyethylgroups (JP-A 5-249682 and JP-A 6-308437), and resins protected witht-butoxycarbonyl groups and 1-alkoxyethyl groups (JP-A 8-123032). Thesechemically amplified resist compositions, however, have their ownproblems. A variety of difficulties arise on the practical applicationof these compositions. Such problems include, for example, environmentalstability, focal latitude, particle, and storage stability.

The environmental stability is generally divided into two categories.One environmental stability is related to the deactivation of aphoto-generated acid by an air-borne base above the resist film or abase beneath the resist film and on the substrate. This phenomenon isoften seen when a photoacid generator capable of generating an acidhaving a high acid strength is used. It is expected that this problem issolved by introducing into the resin acid labile groups which are moreeasy to cleavage by acid or by lowering or weakening the acid strengthof the photo-generated acid. The other environmental stability is thatwhen the period from exposure to post-exposure baking (PEB) isprolonged, which is known as post-exposure delay (PED), thephoto-generated acid diffuses in the resist film so that aciddeactivation may occur when the acid labile groups are less susceptibleto scission and acid decomposition may take place when the acid labilegroups are susceptible to scission, often inviting a change of thepattern profile in either case. For example, this often invites anarrowing or slimming of the line width in the unexposed area in thecase of chemical amplification type, positive working, resistcompositions having acid labile groups mainly of acetal type.

Of the above-referred protective groups, the t-butoxycarbonyl groupshave poor environmental stability on the surface of resist film or onthe substrate (i.e., at the interface between the resist and thesubstrate). As a result, the pattern obtained can have an outwardextending top (T-top profile) or is not sharply defined at all.Alternatively, pattern footing and tapering are sometimes possible. Alsothe resolving power is too low to provide a finer pattern.

The use of 1-alkoxyethyl groups, which have a high resolving power, alsohas problems. As a result of PED, the pattern profile varies to narrowthe line width in the unexposed area (slimming). When the focal point isoffset on a stepped substrate, the pattern on the mask cannot beaccurately transferred to the resist film. Specifically, although arectangular pattern is obtained on accurate focusing, any offsetting ofthe focal point results in the pattern top being noticeably reduced,failing to keep rectangularity. Then the depth of focus is ofsignificance when it is desired to produce a finer pattern. If the depthof focus is narrow, it becomes impossible to form an accurate pattern ona stepped substrate is difficult, and hence to fabricate microelectronicdevices by relying on pattern transfer through etching.

The inventors confirmed that the introduction of a cycloalkyl group suchas cyclohexyloxyethyl into an alkoxyethyl group is effective forimproving the depth of focus. However, probably because of improvedlipophilic property, the adhesion at the pattern-substrate interfacebecomes poor, allowing pattern stripping. Formation of particle in theresist film after development is another problem.

Even when a resin having acid labile groups of at least two types suchas t-butoxycarbonyl and 1-alkoxyalkyl groups is used in a resistcomposition, no satisfactory results are obtained with respect to theabove-described problems, especially resolution and focal latitude.

SUMMARY OF THE INVENTION

An object of the invention is to provide a chemical amplification,positive resist composition having an improved resolution, patternprofile and focal latitude and having eliminated the problems ofadhesion, peeling and defect.

We have found that when a resin which changes its solubility in analkali developer under the action of acid and has substituents of thefollowing general formula (1) is used in combination with a photoacidgenerator, there is formulated a chemical amplification, positive resistcomposition which has an adequate resolution, pattern profile and focallatitude to enable micropatterning. The resulting resist pattern haseliminated the problems of adhesion, stripping, particle and the like.The resist composition is fully effective when processed by deep-UVlithography.

Ph—(CH₂)_(n)OCH(CH₂CH₃)—(1)

Herein Ph is phenyl and n is 1 or 2.

Particularly when the resin which changes its solubility in an alkalideveloper under the action of acid is a polyhydroxystyrene derivative orhydroxystyrene-(meth)acrylic acid copolymer in which some of thehydrogen atoms on phenolic hydroxyl groups and/or carboxyl groups areprotected with substituents of formula (1), the above advantages arefurther enhanced. Better results are obtained upon processing by deep-UVlithography.

According to the invention, there is provided a chemical amplification,positive resist composition comprising

(A) a photoacid generator and

(B) a resin which changes its solubility in an alkali developer underthe action of acid and has substituents of the following general formula(1):

Ph—(CH₂)_(n)OCH(CH₂CH₃)—  (1)

wherein Ph is phenyl and n is 1 or 2.

In one preferred embodiment, the resin (B) is an alkali-soluble resincomprising units of the following formula (2) or (2′) wherein some orall of the hydrogen atoms on phenolic hydroxyl groups and/or carboxylgroups are protected with substituents of the formula (1).

Herein R⁴ is hydrogen or methyl, R⁵ is a straight, branched or cyclicalkyl group of 1 to 8 carbon atoms, x is 0 or a positive integer, y is apositive integer, satisfying x+y≦5, M and N are positive integerssatisfying 0<N/(M+N)≦0.5.

In another preferred embodiment, the resin (B) is a branched,alkali-soluble resin comprising units of the following formula (2″)wherein some of the hydrogen atoms on phenolic hydroxyl groups areprotected with substituents of the formula (1).

Herein R⁴, R⁵, x and y are as defined above, ZZ is a divalent organicgroup selected from the group consisting of CH₂, CH(OH), CR⁵(OH), C═O,and C(OR⁵)(OH), or a trivalent organic group represented by —C(OH)═, Emay be the same or different and is a positive integer, K is a positiveinteger, satisfying 0.001≦K/(K+E)≦0.1, and XX is 1 or 2.

The resin (B) may further has acid labile groups. Specifically, theresin (B) further has acid labile groups which are selected from amonggroups of the following general formulae (4) to (7), tertiary alkylgroups of 4 to 20 carbon atoms, trialkylsilyl groups in which each alkylmoiety has 1 to 6 carbon atoms, and oxoalkyl groups of 4 to 20 carbonatoms.

Herein R¹⁰ and R¹¹ each are hydrogen or a straight, branched or cyclicalkyl group of 1 to 18 carbon atoms, R¹² is a monovalent hydrocarbongroup of 1 to 18 carbon atoms which may contain a hetero atom such asoxygen atom, a pair of R¹⁰ and R¹¹, R¹⁰ and R¹², or R¹¹ and R¹² may forma ring, each of R¹⁰, R¹¹ and R¹² is a straight or branched alkylenegroup of 1 to 18 carbon atoms when they form a ring.

R¹³ is a tertiary alkyl group of 4 to 20 carbon atoms, a trialkylsilylgroup in which each alkyl moiety has 1 to 6 carbon atoms, an oxoalkylgroup of 4 to 20 carbon atoms, or a group of formula (4), z is aninteger of 0 to 6.

R¹⁴ is a straight, branched or cyclic alkyl group of 1 to 8 carbon atomsor a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, his equal to 0 or 1, and i is equal to 0, 1, 2 or 3, satisfying 2h+i=2 or3.

R¹⁵ is a straight, branched or cyclic alkyl group of 1 to 8 carbon atomsor a substituted or unsubstituted aryl group of 6 to 20 carbon atoms,R¹⁶ to R²⁵ are independently hydrogen or monovalent hydrocarbon groupsof 1 to 15 carbon atoms which may contain a hetero atom, R¹⁶ to R²⁵,taken together, may form a ring, and each of R¹⁶ to R²⁵ represents adivalent hydrocarbon group of 1 to 15 carbon atoms which may contain ahetero atom, when they form a ring, or two of R¹⁶ to R²⁵ which areattached to adjoining carbon atoms may bond together directly to form adouble bond.

DESCRIPTION OF THE PREFERRED EMBODIMENT

Resin

The chemical amplification, positive resist composition of the inventionis defined as comprising (A) a photoacid generator and (B) a resin whichchanges its solubility in an alkali developer under the action of acidand has substituents of the following general formula (1):

Ph—(CH₂)_(n)OCH(CH₂CH₃)—  (1)

wherein Ph is phenyl and n is 1 or 2.

The resin which changes its solubility in an alkali developer under theaction of acid and has substituents of formula (1) is described indetail.

The type of the resin is not critical as long as it is an alkali-solubleresin having phenolic hydroxyl groups and/or carboxyl groups in whichsome or all of the hydrogen atoms on phenolic hydroxyl groups and/orhydroxyl groups of carboxyl groups are substituted with substituents offormula (1).

The alkali-soluble resin having phenolic hydroxyl groups and/or carboxylgroups embraces homopolymers and copolymers of p-hydroxystyrene,m-hydroxystyrene, α-methyl-p-hydroxystyrene, 4-hydroxy-2-methylstyrene,4-hydroxy-3-methylstyrene, methacrylic acid and acrylic acid, copolymershaving carboxylic acid derivatives, diphenyl ethylene and analoguesintroduced at the terminus of the foregoing polymers, and branchedcopolymers based on a combination of a hydroxystyrene derivative monomer(as mentioned just above) with a branching monomer such aschloromethylstyrene.

Also included are copolymers obtained by introducing units free of analkali-soluble site (e.g., styrene, α-methylstyrene, acrylates,methacrylates, hydrogenated hydroxystyrene, maleic anhydride, andmaleimide) in addition to the above-mentioned units in such a proportionthat the solubility of the copolymer in an alkali developer is notextremely lowered. The acrylates and methacrylates used herein have anysubstituents which do not undergo acidolysis. Illustrative substituentsare straight, branched or cyclic alkyl groups of 1 to 8 carbon atoms andaromatic groups such as aryl groups, though not limited thereto.

Illustrative examples of the alkali-soluble resin, though not limitedthereto, include poly(p-hydroxystyrene), poly(m-hydroxystyrene),poly(4-hydroxy-2-methylstyrene), poly(4-hydroxy-3-methylstyrene),poly(α-methyl-p-hydroxystyrene), partially hydrogenatedpoly(p-hydroxystyrene) copolymers,p-hydroxystyrene/α-methyl-p-hydroxystyrene copolymers,p-hydroxystyrene/α-methylstyrene copolymers, p-hydroxystyrene/styrenecopolymers, p-hydroxystyrene/m-hydroxystyrene copolymers,p-hydroxystyrene/styrene copolymers, p-hydroxystyrene/acrylic acidcopolymers, p-hydroxystyrene/methacrylic acid copolymers,p-hydroxystyrene/methyl acrylate copolymers, p-hydroxystyrene/acrylicacid/methyl methacrylate copolymers, p-hydroxystyrene/methylmethacrylate copolymers, p-hydroxystyrene/methacrylic acid/methylmethacrylate copolymers, polymethacrylic acid, polyacrylic acid, acrylicacid/methyl acrylate copolymers, methacrylic acid/methyl methacrylatecopolymers, acrylic acid/maleimide copolymers, methacrylicacid/maleimide copolymers, p-hydroxystyrene/acrylic acid/maleimidecopolymers, and p-hydroxystyrene/methacrylic acid/maleimide copolymers,as well as dendritic polymers and hyperbranched polymers of theforegoing phenol derivatives.

Of these polymers, poly(p-hydroxystyrene), partially hydrogenatedpoly(p-hydroxystyrene) copolymers, p-hydroxystyrene/styrene copolymers,p-hydroxystyrene/acrylic acid copolymers, p-hydroxystyrene/methacrylicacid copolymers, and dendritic or hyperbranched polymers ofpoly(p-hydroxystyrene) are preferred.

Especially, alkali-soluble resins comprising units of the followingformula (2), (2′) or (2″) are preferred.

In the formulas, R⁴ is hydrogen or methyl. R⁵ is a straight, branched orcyclic alkyl group of 1 to 8 carbon atoms. Subscript x is 0 or apositive integer, and y is a positive integer, satisfying x+y≦5. M and Nare positive integers satisfying 0<N/(M+N)≦0.5. ZZ is a divalent organicgroup selected from among CH₂, CH(OH), CR⁵(OH), C═O, and C(OR⁵) (OH), ora trivalent organic group represented by —C(OH)═. E, which may be thesame or different, is a positive integer, and K is a positive integer,satisfying 0.001≦K/(K+E)≦0.1. XX is 1 or 2.

These alkali-soluble resins should preferably have a weight averagemolecular weight (Mw) of about 3,000 to about 100,000. Polymers with aMw of less than 3,000 may perform poorly and have low heat resistanceand an insufficient film forming ability. With Mw beyond 100,000,polymers may become less soluble in developers and resist solvents. Thedispersity or polydispersity index (Mw/Mn) of the resin shouldpreferably be up to 3.5, and more preferably up to 1.5. Polymers with adispersity of more than 3.5 often have poor resolution.

It is not critical how to prepare the polymer. In the case ofpoly(p-hydroxystyrene) and similar polymers, living anion polymerizationis recommended because a polymer having a low or narrow dispersity canbe synthesized.

The dendritic or hyperbranched polymer of phenol derivative representedby formula (2″) can be synthesized by effecting living anionpolymerization of a polymerizable monomer such as 4-tert-butoxystyreneand reacting a branching monomer such as chloromethylstyrene asappropriate during the living anion polymerization.

More particularly, living anion polymerization is started using apolymerizable monomer such as 4-tert-butoxystyrene. After apredetermined amount has been polymerized, a branching monomer such aschloromethylstyrene is introduced and reacted with the intermediate.Then the polymerizable monomer such as 4-tert-butoxystyrene and/or thebranching monomer such as chloromethylstyrene is added again forpolymerization. This operation is repeated many times until a desireddendritic or hyperbranched polymer is obtained. If necessary, theprotective groups used to enable living polymerization are deblocked,yielding a dendritic or hyperbranched polymer of phenol derivative.

Examples of the branching monomer are given below.

R⁴, R⁵, x and y are as defined above.

Illustrative examples of the dendritic or hyperbranched polymer arethose having recurring units of the following approximate formulas (8)to (12).

Herein, broken lines represent polymer chains of the phenol derivativemonomer, and D represents units based on the branching monomer. Thenumber of broken line segments between D and D is depicted merely forthe sake of convenience, independent of the number of recurring units inthe polymer chain included between D and D.

The dendritic or hyperbranched polymer of a phenol derivative isprepared by effecting living polymerization of the phenol derivative,reacting with a compound having a polymerizable moiety and a terminatingmoiety and proceeding further polymerization. By repeating thisoperation desired times, a dendritic or hyperbranched polymer of phenolderivative can be synthesized. The living polymerization may be effectedby any desired technique although living anion polymerization ispreferred because of ease of control.

For living anion polymerization to take place, the reaction solvent ispreferably selected from toluene, benzene, tetrahydrofuran, dioxane, anddiethyl ether. Of these, polar solvents such as tetrahydrofuran,dioxane, and diethyl ether are preferable. They may be used alone or inadmixture of two or more.

The initiator used herein is preferably selected from sec-butyl lithium,n-butyl lithium, naphthalene sodium and cumyl potassium. The amount ofthe initiator used is proportional to the design molecular weight.

Preferred reaction conditions include a temperature of −80° C. to 100°C., preferably −70° C. to 0° C., and a time of about 0.1 to 50 hours,preferably about 0.5 to 5 hours.

One exemplary reaction scheme using sec-butyl lithium as the initiatorand 4-chloromethylstyrene as the branching monomer is shown below. Thebranching coefficient can be altered by repeating the reaction step anydesired times.

Herein, R⁴, R⁵, x and y are as defined above, m₁ and m₂ each are 0 or apositive integer, and R is a substituent capable of withstanding livinganion polymerization.

The living polymer thus obtained is deactivated or stopped, and thesubstituent R which has been introduced for the progress of living anionpolymerization is deprotected, obtaining an alkali-soluble resin.

While the resin capable of changing its solubility in an alkalideveloper under the action of acid (B) which is formulated in thechemical amplification positive resist composition has substituents ofthe formula (1), the proportion of substituents (1) in the resin ispreferably about 1 to 40 mol % based on the phenolic hydroxyl groupsand/or carboxyl groups in the starting alkali-soluble resin. Theproportion of substituents (1) is more preferably about 5 to 30 mol %,and most preferably about 10 to 25 mol %. If the proportion ofsubstituents (1) is more than 40 mol %, there may often arise problemswith respect to resist solubility and particle. A proportion ofsubstituents (1) less than 1 mol % may often fail to exert the effectsof the invention.

More illustrative examples are polymers comprising recurring units ofthe above formula (2) or (2″) wherein the hydrogen atoms on phenolichydroxyl groups are replaced by substituents of the above formula (1) ina proportion of more than 1 mol % to 40 mol %, on average, based on theentire hydrogen atoms on phenolic hydroxyl groups, the polymers having aweight average molecular weight of about 3,000 to about 100,000.

Alternatively, polymers comprising recurring units of the above formula(2′), specifically copolymers comprising p-hydroxystyrene and/orα-methyl-p-hydroxystyrene and acrylic acid and/or methacrylic acid, areuseful wherein the hydrogen atoms on carboxyl groups in the acrylic acidand/or methacrylic acid are replaced by substituents of the aboveformula (1) or other acid labile groups, and units based on acrylateand/or methacrylate are present in the polymer in a proportion from morethan 1 mol % to 40 mol % on average, and some of the hydrogen atoms onphenolic hydroxyl groups in the p-hydroxystyrene and/ora-methyl-p-hydroxystyrene may be replaced by substituents of the aboveformula (1). More preferably, the units based on acrylate and/ormethacrylate and the units based on p-hydroxystyrene and/orα-methyl-p-hydroxystyrene having substituents of formula (1) are presentin the polymer in a total proportion from more than 1 molt to 40 molt onaverage.

Such polymers are exemplified by those polymers comprising recurringunits of the following general formula (2a), (2a′) or (2a″) and having aweight average molecular weight of about 3,000 to about 100,000.

In the formulas, R⁴ is hydrogen or methyl. R⁵ is a straight, branched orcyclic alkyl group of 1 to 8 carbon atoms. R⁶ is a substituent of theabove formula (1). R^(6a) is hydrogen or a substituent of formula (1)and/or an acid labile group, and at least some, preferably all, of theR^(6a) groups are substituents of formula (1) and/or acid labile groups.Subscript x is 0 or a positive integer, and y is a positive integer,satisfying x+y<≦5. S and T are positive integers, satisfying0.01≦S/(S+T)≦0.4. The R⁶ groups may be the same or different when y is 2or more. M and N are positive integers, and L is 0 or a positiveinteger, satisfying 0<N/(M+N)≦0.4 and 0.01≦(N+L)/(M+N+L)≦0.4. ZZ is adivalent organic group selected from among CH₂, CH(OH), CR⁵(OH), C═O,and C(OR⁵)(OH), or a trivalent organic group represented by —C(OH)═. Kis a positive integer, satisfying 0.001≦K/(K+S+T)≦0.1. XX is 1 or 2. Theacid labile groups will be described later.

Examples of the straight, branched or cyclic alkyl group of 1 to 8carbon atoms represented by R⁵ include methyl, ethyl, propyl, isopropyl,n-butyl, isobutyl, tert-butyl, cyclohexyl and cyclopentyl.

As compared with conventional resins based on linear polymers, the resinwhich changes its solubility in an alkali developer under the action ofacid, obtained by introducing substituents of formula (1) into thedendritic or hyperbranched polymer, has the advantage that theperformance of chemical amplification positive resist compositions isimproved due to the effects of polymer branching and increased freevolume.

The advantages inherent to the invention are derived by introducingsubstituents of formula (1) into an alkali-soluble resin while theresist performance is dictated by the properties of the originalalkali-soluble resin prior to substitution. Therefore, the originalalkali-soluble resin should be selected in accordance with the desiredproperties.

For example, the dendritic or hyperbranched polymers have a smallermolecular size than linear polymers, which leads to an improvedresolution. When it is desired to improve heat resistance by increasingthe molecular weight of the polymer, this can be accomplished withoutincreasing the viscosity, which leads to an improved process stability.The dendritic polymers have an increased number of terminuses, which iseffective for improving adhesion to substrates.

It is believed that these advantages are due to the effects ofentanglement between polymers. It is believed that polymers are not keptseparate, but form a cluster. In the case of greater or strongerclusters, their size or strength affects the resolution and edgeroughness. It is understood that a linear polymer increases the degreeof entanglement in proportion to the backbone length and forms a greateror stronger cluster. By contrast, the dendritic or hyperbranched polymergives rise to the entanglement of polymer segments corresponding to thelength of branches, independent of the overall length of the polymer,and as a consequence, the likelihood of entanglement between polymersthemselves is retarded. This leads to the advantages of improvedresolution, minimized increase of viscosity even in the case of highmolecular weight one, and improved adhesion.

The resin which changes its solubility in an alkali developer under theaction of acid, obtained by introducing substituents of formula (1) intothe dendritic or hyperbranched polymer, preferably has a weight averagemolecular weight of about 5,000 to about 100,000 and a number ofbranches of 0.001 to 0.1, based on the entire monomer units constitutingthe polymer.

For the synthesis of the resin which changes its solubility in an alkalideveloper under the action of acid and has substituents of formula (1),preferably phenolic hydroxyl groups and/or carboxyl groups in thealkali-soluble resin are reacted with a propenyl ether such as benzylpropenyl ether or phenethyl propenyl ether under acidic conditions. Alsopreferably, synthesis is carried out by reacting the alkali-solubleresin with benzyl or phenethyl 1-halogenated propyl ether such as benzyl1-chloropropyl ether, benzyl 1-bromopropyl ether, phenethyl1-chloropropyl ether or phenethyl 1-bromopropyl ether under basicconditions.

The propenyl ethers can be synthesized in a conventional way whilereferring to Greene, “Protective Groups in Organic Synthesis,” JohnWiley & Sons, 1981. Specifically, benzyl alcohol or 2-phenethyl alcoholis reacted with allyl chloride or allyl bromide under basic conditionsto form an allyl ether. Alternatively, benzyl chloride or 2-phenethylchloride is reacted with allyl alcohol under basic conditions to form anallyl ether. Next, the allyl ether is isomerized through rearrangementinto a propenyl ether. Further, hydrogen chloride or hydrogen bromide isadded to the propenyl ether to form a benzyl or phenethyl halogenatedpropyl ether.

In the formulas, Ph is phenyl, n is as defined above, and X is chlorine,bromine or iodine.

While the resin capable of changing its solubility in an alkalideveloper under the action of acid (B) which is formulated in thechemical amplification positive resist composition has substituents ofthe formula (1), it may further have acid labile groups of one or moretypes. The total of substituents of formula (1) and other acid labilegroups is preferably 1 to 80 mol % based on the phenolic hydroxyl groupsand/or carboxyl groups in the original alkali-soluble resin. This totalis more preferably 5 to 50 mol %, and most preferably 10 to 40 mol %.

Provided that the proportion of substituents of formula (1) relative tothe phenolic hydroxyl groups and/or carboxyl groups in thealkali-soluble resin is A mol % and the proportion of other acid labilegroups relative to the phenolic hydroxyl groups and/or carboxyl groupsis B mol %, it is recommended that A/(A+B) range from 0.1 to 1, morepreferably from 0.3 to 1, and most preferably from 0.5 to 1.

The acid labile groups other than formula (1) are preferably groups ofthe following general formulae (4) to (7), tertiary alkyl groups of 4 to20 carbon atoms, preferably 4 to 15 carbon atoms, trialkylsilyl groupswhose alkyl groups each have 1 to 6 carbon atoms, or oxoalkyl groups of4 to 20 carbon atoms.

Herein R¹⁰ and R¹¹ are independently hydrogen or straight, branched orcyclic alkyl groups of 1 to 18 carbon atoms, preferably 1 to 10 carbonatoms, for example, methyl, ethyl, propyl, isopropyl, n-butyl,sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl andn-octyl. R¹² is a monovalent hydrocarbon group of 1 to 18 carbon atoms,preferably 1 to 10 carbon atoms, which may have a hetero atom (e.g.,oxygen atom), for example, straight, branched or cyclic alkyl groups,and such groups in which some hydrogen atoms are replaced by hydroxyl,alkoxy, oxo, amino or alkylamino groups. Illustrative examples of thesubstituted alkyl groups are given below.

A pair of R¹⁰ and R¹¹, a pair of R¹⁰ and R¹², or a pair of R¹¹ and R¹²,taken together, may form a ring. Each of R¹⁰, R¹¹ and R¹² is a straightor branched alkylene group of 1 to 18 carbon atoms, preferably 1 to 10carbon atoms, when they form a ring.

R¹³ is a tertiary alkyl group of 4 to 20 carbon atoms, preferably 4 to15 carbon atoms, a trialkylsilyl group whose alkyl groups each have 1 to6 carbon atoms, an oxoalkyl group of 4 to 20 carbon atoms or a group offormula (4). Exemplary tertiary alkyl groups are tert-butyl, tert-amyl,1,1-diethylpropyl, 1-methylcyclopentyl, 1-ethylcyclopentyl,1-isopropylcyclopentyl, 1-butylcyclopentyl, 1-methylcyclohexyl,1-ethylcyclohexyl, 1-isopropylcyclohexyl, 1-butylcyclohexyl,1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, and2-methyl-2-adamantyl. Exemplary trialkylsilyl groups are trimethylsilyl,triethylsilyl, and dimethyl-tert-butylsilyl. Exemplary oxoalkyl groupsare 3-oxocyclohexyl, 4-methyl-2-oxooxan-4-yl, and5-methyl-5-oxooxoran-4-yl. Letter z is an integer of 0 to 6.

R¹⁴ is a straight, branched or cyclic alkyl group of 1 to 8 carbon atomsor substituted or unsubstituted aryl group of 6 to 20 carbon atoms.Exemplary straight, branched or cyclic alkyl groups include methyl,ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl,n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, cyclopentylmethyl,cyclopentylethyl, cyclohexylmethyl and cyclohexylethyl. Exemplarysubstituted or unsubstituted aryl groups include phenyl, methylphenyl,naphthyl, anthryl, phenanthryl, and pyrenyl. Letter h is equal to 0 or1, i is equal to 0, 1, 2 or 3, satisfying 2h+i=2 or 3.

R¹⁵ is a straight, branched or cyclic alkyl group of 1 to 8 carbon atomsor substituted or unsubstituted aryl group of 6 to 20 carbon atoms,examples of which are as exemplified for R¹⁴. R¹⁶ to R²⁵ areindependently hydrogen or monovalent hydrocarbon groups of 1 to 15carbon atoms which may contain a hetero atom, for example, straight,branched or cyclic alkyl groups such as methyl, ethyl, propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl,n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, cyclopentylmethyl,cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl,and cyclohexylbutyl, and substituted ones of these groups in which somehydrogen atoms are replaced by hydroxyl, alkoxy, carboxy,alkoxycarbonyl, oxo, amino, alkylamino, cyano, mercapto, alkylthio, andsulfo groups. R¹⁶ to R²⁵, for example, a pair of R¹⁶ and R¹⁷, a pair ofR¹⁶ and R¹⁸, a pair of R¹⁷ and R¹⁹, a pair of R¹⁸ and R¹⁹, a pair of R²⁰and R²¹, or a pair of R²² and R²³, taken together, may form a ring. WhenR¹⁶ to R²⁶ form a ring, they are divalent hydrocarbon groups which maycontain a hetero atom, examples of which are the above-exemplifiedmonovalent hydrocarbon groups with one hydrogen atom eliminated. Also,two of R¹⁶ to R²⁵ which are attached to adjacent carbon atoms (forexample, a pair of R¹⁶ and R¹⁸, a pair of R¹⁸ and R²⁴, or a pair of R²²and R²⁴) may directly bond together to form a double bond.

Of the acid labile groups of formula (4), illustrative examples of thestraight or branched groups are given below.

—CH₂—O—CH₃ —CH₂—O—CH₂—CH₃ —CH₂—O—(CH₂)₂—CH₃

Of the acid labile groups of formula (4), illustrative examples of thecyclic groups include tetrahydrofuran-2-yl,2-methyltetrahydrofuran-2-yl, tetrahydropyran-2-yl and2-methyltetrahydropyran-2-yl.

Illustrative examples of the acid labile groups of formula (5) includetert-butoxycarbonyl, tert-butoxy-carbonylmethyl, tert-amyloxycarbonyl,tert-amyloxycarbonyl-methyl, 1,1-diethylpropyloxycarbonyl,1,1-diethylpropyloxycarbonylmethyl, 1-ethylcyclopentyl-oxycarbonyl,1-ethylcyclopentyloxycarbonylmethyl, 1-ethyl-2-cyclopentenyloxycarbonyl,1-ethyl-2-cyclopentenyl-oxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl,2-tetrahydropyranyloxycarbonylmethyl, and2-tetrahydro-furanyloxycarbonylmethyl.

Illustrative examples of the acid labile groups of formula (6) include1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl,1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1-sec-butylcyclopentyl,1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl,3-ethyl-1-cyclopenten-3-yl, 3-methyl-1-cyclohexen-3-yl, and3-ethyl-1-cyclohexen-3-yl.

Illustrative examples of the acid labile groups of formula (7) are givenbelow.

Exemplary of the tertiary alkyl group of 4 to 20 carbon atoms,preferably 4 to 15 carbon atoms, are tert-butyl, tert-amyl,3-ethyl-3-pentyl and dimethylbenzyl.

Exemplary of the trialkylsilyl groups whose alkyl groups each have 1 to6 carbon atoms are trimethylsilyl, triethylsilyl, andtert-butyldimethylsilyl.

Exemplary of the oxoalkyl groups of 4 to 20 carbon atoms are3-oxocyclohexyl and groups represented by the following formulae.

In an alternative embodiment, the resin capable of changing itssolubility in an alkali developer under the action of acid and havingsubstituents of the formula (1) is a polymer comprising units of formula(2) or (2′) in which some of the hydrogen atoms on phenolic hydroxylgroups are crosslinked within a molecule and/or between molecules in aproportion of more than 0 mol % to 50 mol %, on the average, of theentire phenolic hydroxyl groups in the polymer, with crosslinking groupshaving C—O—C linkages represented by the following general formula (3a)or (3b).

The crosslinking groups having C—O—C linkages may be groups representedby the following general formula (3a) or (3b), preferably the followinggeneral formula (3a′) or (3b′).

Herein, each of R⁷ and R⁸ is hydrogen or a straight, branched or cyclicalkyl group of 1 to 8 carbon atoms, or R⁷ and R⁸, taken together, mayform a ring, and each of R⁷ and R⁸ is a straight or branched alkylenegroup of 1 to 8 carbon atoms when they form a ring. R⁹ is a straight,branched or cyclic alkylene group of 1 to 10 carbon atoms, letter b is 0or an integer of 1 to 10. A is an a-valent aliphatic or alicyclicsaturated hydrocarbon group, aromatic hydrocarbon group or heterocyclicgroup of 1 to 50 carbon atoms, which may be separated by a hetero atomand in which some of the hydrogen atom attached to carbon atoms may bereplaced by hydroxyl, carboxyl, carbonyl or halogen. B is —CO—O—,—NHCO—O— or —NHCONH—. Letter a is an integer of 2 to 8 and a is aninteger of 1 to 7.

Herein, each of R⁷ and R⁸ is hydrogen or a straight, branched or cyclicalkyl group of 1 to 8 carbon atoms, or R⁷ and R⁸, taken together, mayform a ring, and each of R⁷ and R⁸ is a straight or branched alkylenegroup of 1 to 8 carbon atoms when they form a ring. R⁹ is a straight,branched or cyclic alkylene group of 1 to 10 carbon atoms, letter b is 0or an integer of 1 to 5. A is an a″-valent straight, branched or cyclicalkylene, alkyltriyl or alkyltetrayl group of 1 to 20 carbon atoms orarylene group of 6 to 30 carbon atoms, which may be separated by ahetero atom and in which some of the hydrogen atom attached to carbonatoms may be replaced by hydroxyl, carboxyl, acyl or halogen. B is—CO—O—, —NHCO—O— or —NHCONH—. Letter a″ is an integer of 2 to 4 and a′″is an integer of 1 to 3.

Examples of the straight, branched or cyclic C₁₋₈ alkyl grouprepresented by R⁷ and R⁸ are as exemplified for R⁵.

Examples of the straight, branched or cyclic C₁₋₁₀ alkylene grouprepresented by R⁹ include methylene, ethylene, propylene, isopropylene,n-butylene, isobutylene, cyclohexylene, and cyclopentylene.

Exemplary halogen atoms are fluorine, chlorine, bromine and iodine.

Illustrative examples of A are described later. These crosslinkinggroups of formulae (3a) and (3b) originate from alkenyl ether compoundsand halogenated alkyl ether compounds to be described later.

As understood from the value of a′ in formula (3a) or (3b), thecrosslinking group is not limited to a divalent one and trivalent tooctavalent groups are acceptable. For example, the divalent crosslinkinggroup is exemplified by groups of the following formulas (3a″) and(3b″), and the trivalent crosslinking group is exemplified by groups ofthe following formulas (3a′″) and (3b′″).

R⁷, R⁸, R⁹, A, B and b are as defined above.

In a further alternative embodiment, the resin capable of changing itssolubility in an alkali developer under the action of acid and havingsubstituents of the formula (1) is a polymer comprising recurring unitsof the following general formula (2b), (2b′) or (2b″), and morepreferably the same polymer in which hydrogen atoms on phenolic hydroxylgroups represented by R are eliminated to leave oxygen atoms which arecrosslinked within a molecule and/or between molecules with crosslinkinggroups having C—O—C linkages represented by the above formula (3a) or(3b).

Herein, R represents an acid labile group, attached to an oxygen atom,other than the substituent of formula (1) or a crosslinking group havingC—O—C linkages, attached to an oxygen atom, represented by the aboveformula (3a) or (3b). R⁴ is hydrogen or methyl, R⁵ is a straight,branched or cyclic alkyl group of 1 to 8 carbon atoms. R¹³ is a tertiaryalkyl group of 4 to 20 carbon atoms, an aryl-substituted alkyl group of7 to 20 carbon atoms, an oxoalkyl group of 4 to 20 carbon atoms or agroup represented by —CR¹⁰R¹¹OR¹². R¹⁰ and R¹¹ are independentlyhydrogen or straight, branched or cyclic alkyl groups of 1 to 18 carbonatoms, R¹² is a monovalent hydrocarbon group of 1 to 18 carbon atomswhich may have a hetero atom, or R¹⁰ and R¹¹, R¹⁰ and R¹², or R¹″ andR¹², taken together, may form a ring, with the proviso that each of R¹⁰,R¹¹ and R¹² is a straight or branched alkylene group of 1 to 18 carbonatoms when they form a ring. Letter zz is an integer of 0 to 6. S1 is apositive number, each of S2, T1, and T2 is 0 or a positive number,satisfying 0≦T1/(S1+T1+T2+S2)≦0.8, 0.01≦S1/(S1+T1+T2+S2)≦0.4,0≦T2/(S1+T1+T2+S2)≦0.09, and 0.01≦(S1+S2)/(S1+T1+T2+S2) ≦0.8. Each of uand w is 0 or a positive integer, and v is a positive integer,satisfying u+v+w≦5. Letters m, x and y are as defined above.

More preferably, S1, S2, T1 and T2 satisfy the ranges:0≦T1/(S1+T1+T2+S2)≦0.3, 0.05≦S1/(S1+T1+T2+S2)≦0.3,0≦S2/(S1+T1+T2+S2)≦0.3, 0.5≦T2/(S1+T1+T2+S2)≦0.95, and0.05≦(S1+S2)/(S1+T1+T2+S2)≦0.5; and most preferably,0≦T1/(S1+T1+T2+S2)≦0.15, 0.1≦S1/(S1+T1+T2+S2)≦0.25,0≦S2/(S1+T1+T2+S2)≦0.15, 0.5≦T2/(S1+T1+T2+S2)≦0.9, and0.1≦(S1+S2)/(S1+T1+T2+S2)≦0.4.

Herein, R represents an acid labile group, attached to an oxygen atom,other than the substituent of formula (1) or a crosslinking group havingC—O—C linkages, attached to an oxygen atom, represented by the aboveformula (3a) or (3b). R⁴ is hydrogen or methyl, R⁵ is a straight,branched or cyclic alkyl group of 1 to 8 carbon atoms. R^(6a) ishydrogen, a substituent of formula (1) or an acid labile group asmentioned above, and at least some, preferably all of the R^(6a) groupsare acid labile groups. R¹³ is a tertiary alkyl group of 4 to 20 carbonatoms, an aryl-substituted alkyl group of 7 to 20 carbon atoms, anoxoalkyl group of 4 to 20 carbon atoms or a group represented by—CR¹⁰R¹¹OR¹². R¹⁰ and R¹¹ are independently hydrogen or straight,branched or cyclic alkyl groups of 1 to 18 carbon atoms, R¹² is amonovalent hydrocarbon group of 1 to 18 carbon atoms which may have ahetero atom, or R¹⁰ and R¹¹, R¹⁰ and R¹², or R¹¹ and R¹², takentogether, may form a ring, with the proviso that each of R¹⁰, R¹¹ andR¹² is a straight or branched alkylene group of 1 to 18 carbon atomswhen they form a ring. Letter z is an integer of 0 to 6. Letters n, u,w, v, x and y are as defined above.

N is a positive number, each of M1, M2, M3 and M4 is 0 or a positivenumber, satisfying 0<N/(M1+M2+M3+M4+N)≦0.4,0.01≦(M3+N)/(M1+M2+M3+M4+N)≦0.5, 0≦M2/(M1+M2+M3+M4+N)≦0.99, andM1+M2+M3+M4+N=1. M1, M3 and M4 are not equal to 0 at the same time. Morepreferably, N, M1, M2, M3 and M4 satisfy the ranges:0<N/(M1+M2+M3+M4+N)<0.3, 0.05≦(M3+N)/(M1+M2+M3+M4+N)≦0.4, and0.5≦M2/(M1+M2+M3+M4+N)≦0.95, and most preferably,0<N/(M1+M2+M3+M4+N)≦0.3, 0.1≦(M3+N)/(M1+M2+M3+M4+N)≦0.3, and0.6≦M2/(M1+M2+M3+M4+N)≦0.9.

In the formula, R, R⁴, R⁵, R³ R¹⁰ R¹, R¹² z, S, 2, T1, T2, u, w, v, n, xand y are as defined above. ZZ is a divalent organic group selected fromthe group consisting of CH₂, CH(OH), CR⁵(OH), C═O, and C(OR⁵)(OH), or atrivalent organic group represented by —C(OH)═. XX is 1 or 2. K is apositive integer satisfying 0.001≦K/(S1+T1+T2+S2+K)≦0.1.

In the embodiment wherein the resin (B) capable of changing itssolubility in an alkali developer under the action of acid and havingsubstituents of the formula (1) is crosslinked with acid labilesubstituents, specifically crosslinked within a molecule and/or betweenmolecules with crosslinking groups having C—O—C linkages resulting fromreaction of phenolic hydroxyl groups with an alkenyl ether compound orhalogenated alkyl ether, the proportion of crosslinking groups havingC—O—C linkages is preferably, on the average, from more than 0 mol % to20 mol %, more preferably from 0.2 mol % to 10 mol %. At 0 mol %, fewbenefits of the crosslinking group would be obtained, resulting in areduced contrast of alkali dissolution rate and a low resolution. Withmore than 20 mol %, a too much crosslinked polymer would gel, becomeinsoluble in alkali, induce a film thickness change, internal stressesor bubbles upon alkali development, and lose adhesion to the substratedue to less hydrophilic groups.

The total proportion of substituents of formula (1) and acid labilegroups is preferably, on the average, more than 0 mol % to 50 mol %,especially 10 to 40 mol %. At 0 mol %, there result a reduced contrastof alkali dissolution rate and a low resolution. With more than 50 mol%, the polymer may lose alkali solubility or affinity to an alkalideveloper upon development and have poor resolution.

By properly selecting the proportions of crosslinking groups havingC—O—C linkages and acid labile groups within the above-defined ranges,it becomes possible to control the size and configuration of a resistpattern as desired. In the resist composition according to theinvention, the contents of crosslinking groups having C—O—C linkages andacid labile groups in the polymer have substantial influence on thedissolution rate contrast of a resist film and govern the properties ofthe resist composition relating to the size and configuration of aresist pattern.

Now A in the crosslinking group is described. The (a′+1)-valent organicgroups represented by A include hydrocarbon groups, for example,substituted or unsubstituted alkylene groups preferably having 1 to 50carbon atoms, and especially 1 to 40 carbon atoms, substituted orunsubstituted arylene groups preferably having 6 to 50 carbon atoms, andespecially 6 to 40 carbon atoms (these alkylene and arylene groups mayhave an intervening hetero atom or group such as O, NH, N(CH₃), S orSO₂, and where substituted, the substituents are hydroxyl, carboxyl,acyl and fluorine), and combinations of these alkylene groups with thesearylene groups, and a′-valent groups corresponding to the foregoinggroups from which a hydrogen atom attached to a carbon atom iseliminated (wherein a′ is an integer of 3 to 8). Additional examplesinclude (a′+1)-valent heterocyclic groups, and combinations of theseheterocyclic groups with the foregoing hydrocarbon groups.

Illustrative examples of A are given below.

Preferably, in formula (3a), R⁷ is methyl, R⁸ is hydrogen, b is equal to0, and A is ethylene, 1,4-butylene or 1,4-cyclohexylene.

In preparing the polymer which is crosslinked within a molecular and/orbetween molecules with crosslinking groups having C—O—C linkages,synthesis can be made by reacting a corresponding non-crosslinkedpolymer with an alkenyl ether in the presence of an acid catalyst in aconventional manner.

Alternatively, where decomposition of other acid labile groups takesplace in the presence of an acid catalyst, the end product can besynthesized by first reacting an alkenyl ether with hydrochloric acid orthe like to form a halogenated alkyl ether, and reacting it with apolymer under basic conditions in a conventional manner.

Illustrative, non-limiting, examples of the alkenyl ether includeethylene glycol divinyl ether, triethylene glycol divinyl ether,1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether,1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether,tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether,trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether,hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether,1,4-divinyloxymethylcyclohexane, tetraethylene glycol divinyl ether,pentaerythritol divinyl ether, pentaerythritol trivinyl ether,pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitolpentavinyl ether, ethylene glycol diethylene vinyl ether, triethyleneglycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether,triethylene glycol diethylene vinyl ether, trimethylolpropanetriethylene vinyl ether, trimethylolpropane diethylene vinyl ether,pentaerythritol diethylene vinyl ether, pantaerythritol triethylenevinyl ether, pentaerythritol tetraethylene vinyl ether, and thecompounds of the following formulae (I-1) through (I-31).

Also useful are terephthalic acid diethylene vinyl ether, phthalic aciddiethylene vinyl ether, isophthalic acid diethylene vinyl ether,phthalic acid dipropylene vinyl ether, terephthalic acid dipropylenevinyl ether, isophthalic acid dipropylene vinyl ether, maleic aciddiethylene vinyl ether, fumaric acid diethylene vinyl ether, itaconicacid diethylene vinyl ether as well as the compounds of the followingformulae (II-1) through (II-11). Useful alkenyl ethers are not limitedto these examples.

In the resist composition according to the invention, the resin used ascomponent (B) is as described above. When the resin has acid labilegroups other than formula (1), the preferred acid labile groups are1-ethylcyclopentyl, 1-ethylcyclohexyloxycarbonylmethyl, tert-amyl,1-ethoxyethyl, 1-ethoxypropyl, tetrahydrofuranyl, tetrahydropyranyl,tert-butyl, 1-ethylcyclohexyl, tert-butoxycarbonyl,tert-butoxy-carbonylmethyl groups, and substituents of formula (3a)wherein R⁷ is methyl, R⁸ is hydrogen, b is equal to 0, and A isethylene, 1,4-butylene or 1,4-cyclohexylene.

In a single polymer, these substituents may be incorporated alone or inadmixture of two or more types. A blend of two or more polymers havingsubstituents of different types is also acceptable.

The percent proportion of these substituents substituting for phenol andcarboxyl groups in the polymer is not critical. Preferably the percentsubstitution is selected such that when a resist composition comprisingthe polymer is applied onto a substrate to form a coating, the unexposedarea of the coating may have a dissolution rate of 0.01 to 10 Å/sec in a2.38% tetramethylammonium hydroxide (TMAH) developer.

On use of a polymer containing a greater proportion of carboxyl groupswhich can reduce the alkali dissolution rate, the percent substitutionmust be increased or non-acid-labile substituents to be described latermust be introduced.

When acid labile groups for intramolecular and/or intermolecularcrosslinking are to be introduced, the percent proportion ofcrosslinking substituents is preferably up to 20%, more preferably up to10%. If the percent substitution of crosslinking substituents is toohigh, crosslinking results in a higher molecular weight which canadversely affect dissolution, stability and resolution. It is alsopreferred to further introduce another non-crosslinking acid labilegroup into the crosslinked polymer at a percent substitution of up to10% for adjusting the dissolution rate to fall within the above range.

In the case of poly(p-hydroxystyrene), the optimum percent substitutiondiffers between a substituent having a strong dissolution inhibitoryaction such as a tert-butoxycarbonyl group and a substituent having aweak dissolution inhibitory action such as an acetal group although theoverall percent substitution is preferably 10 to 40%, more preferably 20to 30%.

Polymers having such acid labile groups introduced therein shouldpreferably have a weight average molecular weight (Mw) of about 3,000 toabout 100,000. With a Mw of less than 3,000, polymers would performpoorly and often lack heat resistance and film formability. Polymerswith a Mw of more than 100,000 would be less soluble in a developer anda resist solvent.

Where non-crosslinking acid labile groups are introduced, the polymershould preferably have a dispersity (Mw/Mn) of up to 3.5, preferably upto 1.5. A polymer with a dispersity of more than 3.5 often results in alow resolution. Where crosslinking acid labile groups are introduced,the starting alkali-soluble resin should preferably have a dispersity(Mw/Mn) of up to 1.5, and the dispersity is kept at 3 or lower evenafter protection with crosslinking acid labile groups. If the dispersityis higher than 3, dissolution, coating, storage stability and/orresolution is often poor.

To impart a certain function, suitable substituent groups may beintroduced into some of the phenolic hydroxyl and carboxyl groups on theacid labile group-protected polymer. Exemplary are substituent groupsfor improving adhesion to the substrate, non-acid-labile groups foradjusting dissolution in an alkali developer, and substituent groups forimproving etching resistance. Illustrative, non-limiting, substituentgroups include 2-hydroxyethyl, 2-hydroxypropyl, methoxymethyl,methoxycarbonyl, ethoxycarbonyl, methoxycarbonylmethyl,ethoxycarbonylmethyl, 4-methyl-2-oxo-4-oxoranyl,4-methyl-2-oxo-4-oxanyl, methyl, ethyl, propyl, n-butyl, sec-butyl,acetyl, pivaloyl, adamantyl, isobornyl, and cyclohexyl.

Photoacid Generator (A)

The photoacid generator (A) is a compound capable of generating an acidupon exposure to high energy radiation. Preferred photoacid generatorsare sulfonium salts, iodonium salts, sulfonyldiazomethanes, andN-sulfonyloxyimides. These photoacid generators are illustrated belowwhile they may be used alone or in admixture of two or more.

Sulfonium salts are salts of sulfonium cations with sulfonates.Exemplary sulfonium cations include triphenylsulfonium,(4-tert-butoxyphenyl)diphenylsulfonium,bis(4-tert-butoxyphenyl)phenylsulfonium,tris(4-tert-butoxyphenyl)sulfonium,(3-tert-butoxyphenyl)diphenyl-sulfonium,bis(3-tert-butoxyphenyl)phenylsulfonium,tris(3-tert-butoxyphenyl)sulfonium,(3,4-di-tert-butoxy-phenyl)diphenylsulfonium,bis(3,4-di-tert-butoxyphenyl)-phenylsulfonium,tris(3,4-di-tert-butoxyphenyl)sulfonium,diphenyl(4-thiophenoxyphenyl)sulfonium,(4-tert-butoxy-carbonylmethyloxyphenyl)diphenylsulfonium,tris(4-tert-butoxycarbonylmethyloxyphenyl)sulfonium,(4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium,tris(4-dimethylaminophenyl)sulfonium, 2-naphthyldiphenylsulfonium,dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium,4-methoxyphenyldimethylsulfonium, trimethylsulfonium,2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, andtribenzylsulfonium. Exemplary sulfonates includetrifluoromethanesulfonate, nonafluorobutanesulfonate,heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate,4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate,4,4-toluenesulfonyloxybenzenesulfonate, naphthalenesulfonate,camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate,butanesulfonate, and methanesulfonate. Sulfonium salts based oncombination of the foregoing examples are included.

Iodinium salts are salts of iodonium cations with sulfonates. Exemplaryiodinium cations are aryliodonium cations including diphenyliodinium,bis(4-tert-butylphenyl)iodonium, 4-tert-butoxyphenylphenyliodonium, and4-methoxyphenylphenyliodonium. Exemplary sulfonates includetrifluoromethanesulfonate, nonafluorobutanesulfonate,heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate,4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate,4,4-toluenesulfonyloxy benzenesulfonate, naphthalenesulfonate,camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate,butanesulfonate, and methanesulfonate. Iodonium salts based oncombination of the foregoing examples are included.

Preferred sulfonium salts are triphenylsulfonium 10-camphorsulfonate,triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium4-(4-toluenesulfonyloxy)-benzenesulfonate, triphenylsulfonium2-trifluoromethylbenzenesulfonate, 4-tert-butoxyphenyldiphenylsulfonium4-toluenesulfonate, 4-tert-butoxyphenyldiphenylsulfonium10-camphorsulfonate, 4-tert-butoxyphenyldiphenylsulfoniumpentafluorobenzenesulfonate, 4-tert-butylphenyldiphenylsulfoniumnonafluorobutanesulfonate, 4-tert-butylphenyldiphenylsulfonium4-toluenesulfonate, diphenyl-4-methylphenylsulfonium4-(4-toluenesulfonyloxy)benzenesulfonate,tris(4-tert-butylphenyl)sulfonium 10-camphorsulfonate,tris(4-tert-butylphenyl)sulfonium pentafluorobenzenesulfonate,tris(4-methylphenyl)sulfonium nonafluorobutanesulfonate,tris(4-methylphenyl)sulfonium heptadecaoctanesulfonate, anddiphenylmethylsulfonium nonafluorobutanesulfonate, though not limitedthereto. Preferred iodonium salts are bis(4-tert-butylphenyl)iodonium10-camphorsulfonate, bis(4-tert-butylphenyl)iodoniumnonafluorobutanesulfonate, bis(4-tert-butylphenyl)iodoniumpentafluorobenzenesulfonate, and bis(4-tert-butylphenyl)iodonium4-(4-toluenesulfonyloxy)-benzenesulfonate, though not limited thereto.

Exemplary sulfonyldiazomethane compounds include bissulfonyldiazomethanecompounds and sulfonyl-carbonyldiazomethane compounds such asbis(ethylsulfonyl)-diazomethane,bis(1-methylpropylsulfonyl)diazomethane,bis(2-methylpropylsulfonyl)diazomethane,bis(1,1-dimethylethylsulfonyl)diazomethane,bis(cyclohexylsulfonyl)-diazomethane,bis(perfluoroisopropylsulfonyl)diazomethane,bis(phenylsulfonyl)diazomethane,bis(4-methylphenylsulfonyl)diazomethane,bis(2,4-dimethylphenylsulfonyl)diazomethane,bis(2-naphthylsulfonyl)-diazomethane,4-methylphenylsulfonylbenzoyldiazomethane,tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane,2-naphthylsulfonylbenzoyldiazomethane,4-methylphenylsulfonyl-2-naphthoyldiazomethane,methylsulfonylbenzoyldiazomethane, andtert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane.

N-sulfonyloxyimide photoacid generators include combinations of imideskeletons with sulfonates. Exemplary imide skeletons are succinimide,naphthalene dicarboxylic acid imide, phthalimide, cyclohexyldicarboxylicacid imide, 5-norbornene-2,3-dicarboxylic acid imide, and7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid imide. Exemplarysulfonates include trifluoromethanesulfonate, nonafluorobutanesulfonate,heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate,4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate,naphthalenesulfonate, camphorsulfonate, octanesulfonate,dodecylbenzenesulfonate, butanesulfonate, and methanesulfonate.

Benzoinsulfonate photoacid generators include benzoin tosylate, benzoinmesylate, and benzoin butanesulfonate.

Pyrogallol trisulfonate type photoacid generators include pyrogallol,phloroglucinol, catechol, resorcinol, hydroquinone, in which all thehydroxyl groups are replaced by trifluoromethanesulfonate,nonafluorobutanesulfonate, heptadecafluorooctanesulfonate,2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate,4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate,toluenesulfonate, benzenesulfonate, naphthalenesulfonate,camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate,butanesulfonate, and methanesulfonate.

Nitrobenzyl sulfonate photoacid generators include 2,4-dinitrobenzylsulfonate, 2-nitrobenzyl sulfonate, and 2,6-dinitrobenzyl sulfonate,with exemplary sulfonates including trifluoromethanesulfonate,nonafluorobutanesulfonate, heptadecafluorooctanesulfonate,2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate,4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate,toluenesulfonate, benzenesulfonate, naphthalenesulfonate,camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate,butanesulfonate, and methanesulfonate. Also useful are analogousnitrobenzyl sulfonate compounds in which the nitro group on the benzylside is replaced by a trifluoromethyl group.

Sulfone photoacid generators include bis(phenylsulfonyl)methane,bis(4-methylphenylsulfonyl)methane, bis(2-naphthylsulfonyl)methane,2,2-bis(phenylsulfonyl)propane, 2,2-bis(4-methylphenylsulfonyl)propane,2,2-bis(2-naphthylsulfonyl)propane,2-methyl-2-(p-toluenesulfonyl)propiophenone,2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, and2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one.

Photoacid generators in the form of glyoxime derivatives includebis-o-(p-toluenesulfonyl)-α-dimethylglyoxime,bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime,bis-o-(p-toluenesulfonyl)-α-dicyclohexyl-glyoxime,bis-o-(p-toluenesulfonyl)-2,3-pentanedioneglyoxime,bis-o-(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime,bis-o-(n-butanesulfonyl)-α-dimethylglyoxime,bis-o-(n-butanesulfonyl)-α-diphenylglyoxime,bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime,bis-o-(n-butane-sulfonyl)-2,3-pentanedioneglyoxime,bis-o-(n-butane-sulfonyl)-2-methyl-3,4-pentanedioneglyoxime,bis-o-(methanesulfonyl)-α-dimethylglyoxime,bis-o-(trifluoro-methanesulfonyl)-α-dimethylglyoxime,bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime,bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime,bis-o-(perfluoro-octanesulfonyl)-α-dimethylglyoxime,bis-o-(cyclohexyl-sulfonyl)-α-dimethylglyoxime,bis-o-(benzenesulfonyl)-α-dimethylglyoxime,bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime,bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime,bis-o-(xylenesulfonyl)-α-dimethylglyoxime, andbis-o-(camphorsulfonyl)-α-dimethylglyoxime.

Of these photoacid generators, the sulfonium salts,bissulfonyldiazomethane compounds, and N-sulfonyloxyimide compounds arepreferred.

While the anion of the optimum acid to be generated differs depending onthe ease of scission of acid labile groups introduced in the polymer, ananion which is non-volatile and not extremely diffusive is generallychosen. The preferred anions include benzenesulfonic acid anions,toluenesulfonic acid anions, 4,4-toluenesulfonyloxybenzenesulfonic acidanions, pentafluorobenzenesulfonic acid anions,2,2,2-trifluoroethanesulfonic acid anions, nonafluorobutanesulfonic acidanions, heptadecafluorooctanesulfonic acid anions, and camphorsulfonicacid anions.

In the chemically amplified positive resist composition, an appropriateamount of the photoacid generator (A) is from more than 0 part to 20parts, and especially 1 to 10 parts by weight per 100 parts by weight ofthe base resin in the composition. The photoacid generators may be usedalone or in admixture of two or more. The transmittance of the resistfilm can be controlled by using a photoacid generator having a lowtransmittance at the exposure wavelength and adjusting the amount of thephotoacid generator added.

Resist Composition

As defined above, the chemical amplification, positive resistcomposition of the invention is comprised of (A) the photoacid generatorand (B) the resin which changes its solubility in an alkali developerunder the action of acid and has substituents of formula (1).Illustrative embodiments of the invention are given below although theinvention is not limited thereto.

Embodiment 1 is a chemical amplification, positive resist compositioncomprising (A) the photoacid generator, (B) the resin which changes itssolubility in an alkali developer under the action of acid and hassubstituents of formula (1), and (G) an organic solvent.

Embodiment 2 is a chemical amplification, positive resist composition asset forth as Embodiment 1 and further comprising (C) a resin whichchanges its solubility in an alkali developer under the action of acidand is free of substituents of formula (1).

Embodiment 3 is a chemical amplification, positive resist composition asset forth as Embodiment 1 or 2 and further comprising (D) a basiccompound.

Embodiment 4 is a chemical amplification, positive resist composition asset forth as Embodiment 1, 2 or 3 and further comprising (E) an organicacid derivative.

Embodiment 5 is a chemical amplification, positive resist composition asset forth as Embodiment 1, 2, 3 or 4 and further comprising (F) acompound with a molecular weight of up to 3,000 which changes itssolubility in an alkali developer under the action of acid.

The respective components are described below.

Component (G)

Component (G) is an organic solvent. Illustrative, non-limiting,examples include butyl acetate, amyl acetate, cyclohexyl acetate,3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone,cyclohexanone, cyclopentanone, 3-ethoxyethyl propionate, 3-ethoxymethylpropionate, 3-methoxymethyl propionate, methyl acetoacetate, ethylacetoacetate, diacetone alcohol, methyl pyruvate, ethyl pyruvate,propylene glycol monomethyl ether, propylene glycol monoethyl ether,propylene glycol monomethyl ether propionate, propylene glycol monoethylether propionate, ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, diethylene glycol monomethyl ether, diethylene glycolmonoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone,dimethyl sulfoxide, y-butyrolactone, propylene glycol methyl etheracetate, propylene glycol ethyl ether acetate, propylene glycol propylether acetate, methyl lactate, ethyl lactate, propyl lactate, andtetramethylene sulfone. Of these, the propylene glycol alkyl etheracetates and alkyl lactates are especially preferred. The solvents maybe used alone or in admixture of two or more. An exemplary usefulsolvent mixture is a mixture of a propylene glycol alkyl ether acetateand an alkyl lactate. It is noted that the alkyl groups of the propyleneglycol alkyl ether acetates are preferably those of 1 to 4 carbon atoms,for example, methyl, ethyl and propyl, with methyl and ethyl beingespecially preferred. Since the propylene glycol alkyl ether acetatesinclude 1,2-and 1,3-substituted ones, each includes three isomersdepending on the combination of substituted positions, which may be usedalone or in admixture. It is also noted that the alkyl groups of thealkyl lactates are preferably those of 1 to 4 carbon atoms, for example,methyl, ethyl and propyl, with methyl and ethyl being especiallypreferred.

When the propylene glycol alkyl ether acetate is used as the solvent, itpreferably accounts for at least 50% by weight of the entire solvent.Also when the alkyl lactate is used as the solvent, it preferablyaccounts for at least 50% by weight of the entire solvent. When amixture of propylene glycol alkyl ether acetate and alkyl lactate isused as the solvent, this mixture preferably accounts for at least 50%by weight of the entire solvent. In this solvent mixture, it is furtherpreferred that the propylene glycol alkyl ether acetate is 60 to 95% byweight and the alkyl lactate is 40 to 5% by weight. A lower proportionof the propylene glycol alkyl ether acetate would invite a problem ofinefficient coating whereas a higher proportion thereof would provideinsufficient dissolution and allow for particle and particle formation.A lower proportion of the alkyl lactate would provide insufficientdissolution and cause the problem of many particles and particle whereasa higher proportion thereof would lead to a composition which has a toohigh viscosity to apply and loses storage stability.

Usually the solvent is used in amounts of about 300 to 2,000 parts,preferably about 400 to 1,000 parts by weight per 100 parts by weight ofthe base resin in the chemically amplified positive resist composition.The concentration is not limited to this range as long as film formationby existing methods is possible.

Other Resin (C)

A resin which changes its solubility in an alkali developer under theaction of acid and is free of substituents of formula (1) may be addedas component (C) to the chemically amplified positive resist compositionin addition to the resin (B) which changes its solubility in an alkalideveloper under the action of acid and has substituents of formula (1).

Though not critical, the resin (C) which changes its solubility in analkali developer under the action of acid and is free of substituents offormula (1) is preferably selected from those alkali-soluble resins asdescribed previously in connection with component (B) having introducedtherein acid labile groups as described above in connection withcomponent (B), for example, groups of the above formulas (4) to (7),tertiary alkyl groups with 4 to 20 carbon atoms, preferably with 4 to 15carbon atoms, trialkylsilyl groups whose alkyl groups each have 1 to 6carbon atoms, and oxoalkyl groups of 4 to 20 carbon atoms.

Preferred are resins in the form of poly(p-hydroxystyrene) andp-hydroxystyrene/(meth)acrylic acid copolymers in which some of thehydrogen atoms on phenolic hydroxyl groups and/or carboxyl groups arereplaced by acid labile groups of one or more types.

Illustrative preferred acid labile groups are 1-akoxyalkyl,tert-alkyloxycarbonyl, tert-alkyl, 2-tetrahydropyranyl and2-tetrahydrofuranyl groups.

Preferred combinations of two or more types of acid labile groups arecombinations of different acetal groups, combinations of groupsdiffering in ease of cleavage under the action of acid, such as acetalwith tert-butoxy, combinations of a crosslinking acid labile group withacetal, and combinations of a crosslinking acid labile group with agroup differing in ease of cleavage under the action of acid, such astert-butoxy.

The proportion of the resin (B) which changes its solubility in analkali developer under the action of acid and has substituents offormula (1) to the resin (C) which changes its solubility in an alkalideveloper under the action of acid and is free of substituents offormula (1) is not critical. When the resin (C) is added, it isrecommended that the content of the resin (C) is 0 to 99% by weight,especially 1 to 50% by weight based on the resins (B) and (C) combined.

Basic Compound (D)

The basic compound (D) is preferably a compound capable of suppressingthe rate of diffusion when the acid generated by the photoacid generatordiffuses within the resist film. The inclusion of this type of basiccompound holds down the rate of acid diffusion within the resist film,resulting in better resolution. In addition, it suppresses changes insensitivity following exposure and reduces substrate and environmentdependence, as well as improving the exposure latitude and the patternprofile.

Examples of basic compounds include primary, secondary, and tertiaryaliphatic amines, mixed amines, aromatic amines, heterocyclic amines,carboxyl group-bearing nitrogenous compounds, sulfonyl group-bearingnitrogenous compounds, hydroxyl group-bearing nitrogenous compounds,hydroxyphenyl group-bearing nitrogenous compounds, alcoholic nitrogenouscompounds, amide derivatives, and imide derivatives.

Examples of suitable primary aliphatic amines include ammonia,methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,isobutylamine, sec-butylamine, tert-butylamine, pentylamine,tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine,heptylamine, octylamine, nonylamine, decylamine, dodecylamine,cetylamine, methylenediamine, ethylenediamine, andtetraethylenepentamine. Examples of suitable secondary aliphatic aminesinclude dimethylamine, diethylamine, di-n-propylamine, diisopropylamine,di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine,dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine,dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine,N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, andN,N-dimethyltetraethylene-pentamine. Examples of suitable tertiaryaliphatic amines include trimethylamine, triethylamine,tri-n-propylamine, triisopropylamine, tri-n-butylamine,triisobutylamine, tri-sec-butylamine, tripentylamine,tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine,trioctylamine, trinonylamine, tridecylamine, tridodecylamine,tricetylamine, N,N,N′,N′-tetramethylmethylenediamine,N,N,N′,N′-tetramethylethylenediamine, andN,N,N′,N′-tetramethyltetraethylenepentamine.

Examples of suitable mixed amines include dimethylethylamine,methylethylpropylamine, benzylamine, phenethylamine, andbenzyldimethylamine. Examples of suitable aromatic and heterocyclicamines include aniline derivatives (e.g., aniline, N-methylaniline,N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline,3-methylaniline, 4-methylaniline, ethylaniline, propylaniline,trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline,2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, andN,N-dimethyltoluidine), diphenyl(p-tolyl)amine, methyldiphenylamine,triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene,pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole,2,4-dimethylpyrrole, 2,5-dimethylpyrrole, and N-methylpyrrole), oxazolederivatives (e.g., oxazole and isooxazole), thiazole derivatives (e.g.,thiazole and isothiazole), imidazole derivatives (e.g., imidazole,4-methylimidazole, and 4-methyl-2-phenylimidazole), pyrazolederivatives, furazan derivatives, pyrroline derivatives (e.g., pyrrolineand 2-methyl-1-pyrroline), pyrrolidine derivatives (e.g., pyrrolidine,N-methylpyrrolidine, pyrrolidinone, and N-methylpyrrolidone),imidazoline derivatives, imidazolidine derivatives, pyridine derivatives(e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine,butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine,trimethylpyridine, triethylpyridine, phenylpyridine,3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine,benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine,1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine,2-(1-ethylpropyl)pyridine, aminopyridine, and dimethylaminopyridine),pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives,pyrazoline derivatives, pyrazolidine derivatives, piperidinederivatives, piperazine derivatives, morpholine derivatives, indolederivatives, isoindole derivatives, 1H-indazole derivatives, indolinederivatives, quinoline derivatives (e.g., quinoline and3-quinolinecarbonitrile), isoquinoline derivatives, cinnolinederivatives, quinazoline derivatives, quinoxaline derivatives,phthalazine derivatives, purine derivatives, pteridine derivatives,carbazole derivatives, phenanthridine derivatives, acridine derivatives,phenazine derivatives, 1,10-phenanthroline derivatives, adeninederivatives, adenosine derivatives, guanine derivatives, guanosinederivatives, uracil derivatives, and uridine derivatives.

Examples of suitable carboxyl group-bearing nitrogenous compoundsinclude aminobenzoic acid, indolecarboxylic acid, and amino acidderivatives (e.g. nicotinic acid, alanine, alginine, aspartic acid,glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine,methionine, phenylalanine, threonine, lysine,3-aminopyrazine-2-carboxylic acid, and methoxyalanine). Examples ofsuitable sulfonyl group-bearing nitrogenous compounds include3-pyridinesulfonic acid and pyridinium p-toluenesulfonate. Examples ofsuitable hydroxyl group-bearing nitrogenous compounds, hydroxyphenylgroup-bearing nitrogenous compounds, and alcoholic nitrogenous compoundsinclude 2-hydroxypyridine, aminocresol, 2,4-quinolinediol,3-indolemethanol hydrate, monoethanolamine, diethanolamine,triethanolamine, N-ethyldiethanolamine, N,N-diethyl-ethanolamine,truisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol,3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine,2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine,1-[2-(2-hydroxyethoxy)ethyl]-piperazine, piperidine ethanol,1-(2-hydroxyethyl)-pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidinone,3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol,8-hydroxyjulolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridine ethanol, N-(2-hydroxyethyl)phthalimide, andN-(2-hydroxyethyl)-isonicotinamide. Examples of suitable amidederivatives include formamide, N-methylformamide, N,N-dimethylformamide,acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, andbenzamide. Suitable imide derivatives include phthalimide, succinimide,and maleimide.

Also useful are substituted ones of the hydroxyl group-bearingnitrogenous compounds in which some or all of the hydrogen atoms onhydroxyl groups are replaced by methyl, ethyl, methoxymethyl,methoxyethoxymethyl, acetyl, or ethoxyethyl groups. Preferred aremethyl-, acetyl-, methoxymethyl- and methoxyethoxymethyl-substitutedcompounds of ethanolamine, diethanolamine and triethanolamine. Examplesinclude tris(2-methoxyethyl)amine, tris(2-ethoxyethyl)amine,tris(2-acetoxyethyl)amine, tris{2-(methoxymethoxy)ethyl}amine,tris{2-(methoxyethoxy)-ethyl}amine,tris[2-{(2-methoxyethoxy)methoxy}ethyl]amine,tris{2-(2-methoxyethoxy)ethyl}amine,tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine,tris{2-(1-ethoxypropoxy)-ethyl}amine, andtris[2-{(2-hydroxyethoxy)ethoxy}ethyl]amine.

The basic compounds may be used alone or in admixture of two or more.The basic compound is preferably formulated in an amount of 0 to 2parts, and especially 0.01 to 1 part by weight, per 100 parts by weightof the base resin in the resist composition. The use of more than 2parts of the basis compound would result in too low a sensitivity.

Organic Acid Derivative (E)

Illustrative, non-limiting, examples of the organic acid derivatives (E)include phenol, cresol, catechol, resorcinol, pyrogallol,phloroglucinol, bis(4-hydroxyphenyl)methane,2,2-bis(4′-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone,1,1,1-tris(4′-hydroxyphenyl)ethane, 1,1,2-tris(4′-hydroxyphenyl)ethane,hydroxybenzophenone, 4-hydroxyphenylacetic acid, 3-hydroxyphenylaceticacid, 2-hydroxyphenylacetic acid, 3-(4-hydroxyphenyl)propionic acid,3-(2-hydroxyphenyl)propionic acid, 2,5-dihydroxyphenylacetic acid,3,4-dihydroxyphenylacetic acid, 1,2-phenylenediacetic acid,1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid,1,2-phenylenedioxydiacetic acid, 1,4-phenylenedipropanoic acid, benzoicacid, salicylic acid, 4,4-bis(4′-hydroxyphenyl)valeric acid,4-tert-butoxyphenylacetic acid, 4-(4-hydroxyphenyl)butyric acid,3,4-dihydroxymandelic acid, and 4-hydroxymandelic acid. Of these,salicylic acid and 4,4-bis(41-hydroxyphenyl)valeric acid are preferred.They may be used alone or in admixture of two or more.

In the resist composition, the organic acid derivative is preferablyformulated in an amount of up to 5 parts, and especially up to 1 part byweight, per 100 parts by weight of the base resin in the resistcomposition. The use of more than 5 parts of the organic acid derivativewould result in too low a resolution. Depending on the combination ofthe other components in the resist composition, the organic acidderivative may be omitted.

Component (F)

In one preferred embodiment, the resist composition further contains (F)a compound with a molecular weight of up to 3,000 which changes itssolubility in an alkaline developer under the action of an acid, thatis, a dissolution inhibitor. Typically, a compound obtained by partiallyor entirely substituting acid labile substituents on a phenol orcarboxylic acid derivative having a molecular weight of up to 2,500 isadded as the dissolution inhibitor.

Examples of the phenol or carboxylic acid derivative having a molecularweight of up to 2,500 include bisphenol A, bisphenol H, bisphenol S,4,4-bis(4′-hydroxyphenyl)valeric acid, tris(4-hydroxyphenyl)methane,1,1,1-tris(4′-hydroxyphenyl)ethane, 1,1,2-tris(4′-hydroxyphenyl)ethane,phenolphthalein, and thimolphthalein. The acid labile substituents arethe same as those exemplified as the acid labile groups in the polymer.

Illustrative, non-limiting, examples of the dissolution inhibitors whichare useful herein include

bis(4-(2′-tetrahydropyranyloxy)phenyl)methane,

bis(4-(2′-tetrahydrofuranyloxy)phenyl)methane,

bis(4-tert-butoxyphenyl)methane,

bis (4-tert-butoxycarbonyloxyphenyl)methane,

bis(4-tert-butoxycarbonylmethyloxyphenyl)methane,

bis(4-(1′-ethoxyethoxy)phenyl)methane,

bis(4-(1′-ethoxypropyloxy)phenyl)methane,

2,2-bis(4′-(2″-tetrahydropyranyloxy))propane,

2,2-bis(4′-(2″-tetrahydrofuranyloxy)phenyl)propane,

2,2-bis(4′-tert-butoxyphenyl)propane,

2,2-bis(4′-tert-butoxycarbonyloxyphenyl)propane,

2,2-bis(4′-tert-butoxycarbonylmethyloxyphenyl)propane,

2,2-bis(4′-(1″-ethoxyethoxy)phenyl)propane,

2,2-bis(4′-(1″-ethoxypropyloxy)phenyl)propane,

tert-butyl 4,4-bis(4′-(2″-tetrahydropyranyloxy)phenyl)-valerate,

tert-butyl 4,4-bis(4′-(2″-tetrahydrofuranyloxy)phenyl)-valerate,

tert-butyl 4,4-bis(4′-tert-butoxyphenyl)valerate,

tert-butyl 4,4-bis(4-tert-butoxycarbonyloxyphenyl)valerate,

tert-butyl 4,4-bis(4′-tert-butoxycarbonylmethyloxyphenyl)-valerate,

tert-butyl 4,4-bis(4′-(1″-ethoxyethoxy)phenyl)valerate,

tert-butyl 4,4-bis(4′-(1″-ethoxypropyloxy)phenyl)valerate,

tris(4-(2′-tetrahydropyranyloxy)phenyl)methane,

tris(4-(2′-tetrahydrofuranyloxy)phenyl)methane,

tris(4-tert-butoxyphenyl)methane,

tris(4-tert-butoxycarbonyloxyphenyl)methane,

tris(4-tert-butoxycarbonyloxymethylphenyl)methane,

tris(4-(1′-ethoxyethoxy)phenyl)methane,

tris(4-(1′-ethoxypropyloxy)phenyl)methane,

1,1,2-tris(4′-(2″-tetrahydropyranyloxy)phenyl)ethane,

1,1,2-tris(4′-(2″-tetrahydrofuranyloxy)phenyl)ethane,

1,1,2-tris(4′-tert-butoxyphenyl)ethane,

1,1,2-tris(4′-tert-butoxycarbonyloxyphenyl)ethane,

1,1,2-tris(4′-tert-butoxycarbonylmethyloxyphenyl)ethane,

1,1,2-tris(4′-(1′-ethoxyethoxy)phenyl)ethane, and

1,1,2-tris(4′-(1′-ethoxypropyloxy)phenyl)ethane.

In the resist composition, an appropriate amount of the dissolutioninhibitor is up to 20 parts, and especially up to 15 parts by weight per100 parts by weight of the base resin in the composition. With more than20 parts of the dissolution inhibitor, the resist composition becomesless heat resistant because of an increased content of monomercomponents.

In the chemically amplified positive resist composition of theinvention, there may be added an acid-propagating compound, a surfactantfor improving coating characteristics, and a light absorber for reducingdiffuse reflection from the substrate.

The acid-propagating compound is a compound which is decomposed with anacid to generate an acid. For these compounds, reference should be madeto J. Photopolym. Sci. and Tech., 8, 43-44, 45-46 (1995), and ibid., 9,29-30 (1996).

Examples of the acid-propagating compound includetert-butyl-2-methyl-2-tosyloxymethyl acetoacetate and2-phenyl-2-(tosyloxyethyl)-1,3-dioxoran, but are not limited thereto. Ofwell-known photoacid generators, many of those compounds having poorstability, especially poor thermal stability exhibit an acid-propagatingcompound-like behavior.

In the resist composition, an appropriate amount of the acid-propagatingcompound is up to 2 parts, and especially up to 1 part by weight per 100parts by weight of the base resin in the composition. Excessive amountsof the acid-propagating compound makes diffusion control difficult,leading to degradation of resolution and pattern configuration.

Illustrative, non-limiting, examples of the surfactant include nonionicsurfactants, for example, polyoxyethylene alkyl ethers such aspolyoxyethylene lauryl ether, polyoxyethylene stearyl ether,polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether,polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenolether and polyoxyethylene nonylphenol ether, polyoxyethylenepolyoxypropylene block copolymers, sorbitan fatty acid esters such assorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate,and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylenesorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitantrioleate, and polyoxyethylene sorbitan tristearate; fluorochemicalsurfactants such as EFTOP EF301, EF303 and EF352 (Tohkem Products K.K.),Megaface F171, F172 and F173 (Dai-Nippon Ink & Chemicals K.K.), FloradeFC430 and FC431 (Sumitomo 3M K.K.), Aashiguard AG710, Surflon S-381,S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfynol E1004, KH-10,KH-20, KH-30 and KH-40 (Asahi Glass K.K.); organosiloxane polymersKP341, X-70-092 and X-70-093 (Shin-Etsu Chemical Co., Ltd.), acrylicacid or methacrylic acid Polyflow No. 75 and No. 95 (Kyoeisha UshiKagaku Kogyo K.K.). Inter alia, FC430, Surflon S-381, Surfynol E1004,KH-20 and KH-30 are preferred. These surfactants may be used alone or inadmixture.

In the resist composition, the surfactant is preferably formulated in anamount of up to 2 parts, and especially up to 1 part by weight, per 100parts by weight of the base resin in the resist composition.

In the chemically amplified positive resist composition, a UV absorbermay be added.

Exemplary UV absorbers are fused polycyclic hydrocarbon derivatives suchas pentalene, indene, naphthalene, azulene, heptalene, biphenylene,indacene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene,acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene,pleiadene, picene, perylene, pentaphene, pentacene, benzophenanthrene,anthraquinone, anthrone, benzanthrone, 2,7-dimethoxynaphthalene,2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene,9-ethoxyanthracene, 1,2-naphthoquinone, 9-fluorene, and compounds of thefollowing formulae (D1) and (D2); fused heterocyclic derivatives such asthioxanthen-9-one, thianthrene, dibenzothiophene; benzophenonederivatives such as 2,3,4-trihydroxy-benzophenone,2,3,4,4′-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone,3,5-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone, and4,4′-bis(dimethylamino)-benzophenone; squalic acid derivatives such assqualic acid and dimethyl squalate; diaryl sulfoxide derivatives such asbis(4-hydroxyphenyl) sulfoxide, bis(4-tert-butoxyphenyl) sulfoxide,bis(4-tert-butoxycarbonyloxyphenyl) sulfoxide, andbis[4-(1-ethoxyethoxy)phenyl] sulfoxide; diarylsulfone derivatives suchas bis(4-hydroxyphenyl)sulfone, bis(4-tert-butoxyphenyl)sulfone,bis(4-tert-butoxycarbonyloxyphenyl)-sulfone,bis[4-(1-ethoxyethoxy)phenyl]sulfone, andbis[4-(1-ethoxypropoxy)phenyl]sulfone; diazo compounds such asbenzoquinonediazide, naphthoquinonediazide, anthraquinonediazide,diazofluorene, diazotetralone, and diazophenanthrone; quinonediazidegroup-containing compounds such as complete or partial ester compoundsbetween naphthoquinone-1,2-diazide-5-sulfonic acid chloride and2,3,4-trihydroxybenzophenone and complete or partial ester compoundsbetween naphthoquinone-1,2-diazide-4-sulfonic acid chloride and2,4,4′-trihydroxybenzophenone; tert-butyl 9-anthracenecarboxylate,tert-amyl 9-anthracenecarboxylate, tert-methoxymethyl9-anthracenecarboxylate, tert-ethoxyethyl 9-anthracenecarboxylate,2-tert-tetrahydropyranyl 9-anthracenecarboxylate, and2-tert-tetrahydrofuranyl 9-anthracenecarboxylate.

Herein, R⁶¹ to R⁶³ are independently hydrogen or a straight or branchedalkyl, straight or branched alkoxy, straight or branched alkoxyalkyl,straight or branched alkenyl or aryl group. R⁶⁴ is a substituted orunsubstituted divalent aliphatic hydrocarbon group which may contain anoxygen atom, a substituted or unsubstituted divalent alicyclichydrocarbon group which may contain an oxygen atom, a substituted orunsubstituted divalent aromatic hydrocarbon group which may contain anoxygen atom, or an oxygen atom. R⁶⁵ is an acid labile group as describedabove. Letter J is equal to 0 or 1, EE, F and G are 0 or integers of 1to 9, H is a positive integer of 1 to 10, satisfying EE+F+G+H≦10.

An appropriate amount of UV absorber blended is 0 to 10 parts, morepreferably 0.5 to 10 parts, most preferably 1 to 5 parts by weight per100 parts by weight of the base resin in the resist composition.

For the microfabrication of integrated circuits, any well-knownlithography may be used to form a resist pattern from the chemicalamplification, positive working, resist composition comprising (A) thephotoacid generator and (B) the resin which changes its solubility in analkali developer under the action of acid and has substituents offormula (1) according to the invention.

The composition is applied onto a substrate (e.g., Si, SiO₂, SiN, SiON,TiN, WSi, BPSG, SOG, organic anti-reflecting film, etc.) by a suitablecoating technique such as spin coating, roll coating, flow coating, dipcoating, spray coating or doctor coating. The coating is prebaked on ahot plate at a temperature of 60 to 150° C. for about 1 to 10 minutes,preferably 80 to 120° C. for 1 to 5 minutes. The resulting resist filmis generally 0.1 to 2.0 μm thick. With a mask having a desired patternplaced above the resist film, the resist film is then exposed to actinicradiation, preferably having an exposure wavelength of up to 300 nm,such as UV, deep-UV, electron beams, x-rays, excimer laser light, γ-raysand synchrotron radiation in an exposure dose of about 1 to 200 mJ/cm²,preferably about 10 to 100 mJ/cm². The film is further baked on a hotplate at 60 to 150° C. for 1 to 5 minutes, preferably 80 to 120° C. for1 to 3 minutes (post-exposure baking=PEB).

Thereafter the resist film is developed with a developer in the form ofan aqueous base solution, for example, 0.1 to 5%, preferably 2 to 3%aqueous solution of tetramethylammonium hydroxide (TMAH) for 0.1 to 3minutes, preferably 0.5 to 2 minutes by conventional techniques such asdipping, puddling or spraying. In this way, a desired resist pattern isformed on the substrate. It is appreciated that the resist compositionof the invention is best suited for micro-patterning using such actinicradiation as deep UV with a wavelength of 254 to 193 nm, vacuum UV witha wavelength of 157 nm, electron beams, x-rays, excimer laser light,γ-rays and synchrotron radiation. With any of the above-describedparameters outside the above-described range, the process may sometimesfail to produce the desired pattern.

EXAMPLE

Examples of the invention are given below by way of illustration and notby way of limitation.

Synthesis Example 1

Synthesis of Allyl Benzyl Ether

In 870 g of tetrahydrofuran were dissolved 218 g (2 mol) of benzylalcohol and 224 g (2 mol) of potassium t-butoxide. With stirring at roomtemperature, 242 g (2 mol) of allyl bromide was added dropwise so thatthe temperature might not exceed 60° C. At the end of addition, thesolution was heated at 60° C. on an oil bath and ripened for one hour atthe temperature. The solution was allowed to cool down to roomtemperature, and 11.2 g (0.1 mol) of potassium t-butoxide was added.With stirring at room temperature, 12.1 g (0.1 mol) of allyl bromide wasadded dropwise. The solution was heated at 60° C. on an oil bath andripened for one hour at the temperature. The solution was cooled in anice bath, and 550 g of water was added. The organic layer was collected.The solvent was distilled off in vacuum, yielding 299 g of a crude endproduct. The product was used -in the subsequent reaction withoutfurther purification.

Synthesis Example 2

Synthesis of Benzyl Propenyl Ether

A mixture of 299 g of the crude product, 300 g of dimethyl sulfoxide,and 22.5 g (0.2 mol) of potassium t-butoxide was heated at 100° C. onthe oil bath and ripened for 2 hours at the temperature. The solutionwas allowed to cool, and 650 g of water and 600 g of n-hexane were addedthereto, from which the organic layer was collected. The organic layerwas washed with 250 g of water, and the solvent was distilled off invacuum, leaving 300 g of an oily substance. The oily substance wassubjected to vacuum distillation, obtaining 258 g of the end product,benzyl propenyl ether. The yield was 87% (two steps) and the purity was99.4% as analyzed by gas chromatography.

The results of nuclear magnetic resonance spectroscopy, infraredabsorption spectroscopy and elemental analysis of the compound are shownbelow.

¹H-NMR: CDCl₃ (ppm)

Ha: 1.64-1.67 multiplet 3H Hb: 4.45-4.51 multiplet 1H Hc: 6.03-6.05multiplet 1H Hd: 4.82 singlet 2H Hf: 7.30-7.42 multiplet 5H IR: (cm⁻¹)

3089, 3064, 3034, 2971, 2919, 2868, 1809, 1728, 1668, 1587, 1497, 1454,1404, 1375, 1356, 1290, 1272, 1255, 1207, 1124, 1093, 1074, 1028, 985,957, 908, 732

Elemental analysis for C₁₀H₁₂O₁ (%)

Calcd.C 81.0H 8.2

Found C 81.5H 8.1

Synthesis Example 3

Synthesis of poly(p-(1-benzyloxypropyl)oxystyrene/p-hydroxystyrene)

In 48 g of tetrahydrofuran was dissolved 12 g of poly(p-hydroxystyrene)having a weight average molecular weight (Mw) of 9,000 and a dispersity(Mw/Mn) of 1.05. A catalytic amount of p-toluenesulfonic acid was added.At 10° C., 4.3 g (0.029 mol) of benzyl propenyl ether was added to thesolution, which was stirred for 2 hours. The reaction mixture wasprecipitated from a water/isopropanol mixture, followed by filtrationand drying. The end polymer was obtained in an amount of 13.5 g. On¹H-NMR analysis, the ratio of p-(1-benzyloxypropyl)oxystyrene units top-hydroxystyrene units was approximately 22.5:77.5.

The polymer had a weight average molecular weight (Mw) of about 11,000as analyzed by GPC and calculated on a polystyrene basis and adispersity (Mw/Mn) of 1.10.

Synthesis Example 4

Synthesis of Tri-Branched poly(p-hydroxystyrene)

A 1-liter flask was charged with 500 ml of tetrahydrofuran as a solventand 0.01 mol of sec-butyl lithium as an initiator. To the solution at−78° C. was added 40 g of p-tert-butoxystyrene. With stirring,polymerization reaction was effected for 30 minutes. The reactionsolution turned red. For producing a branched polymer, 0.005 mol ofp-chloromethylstyrene was added to the reaction solution whereuponreaction was effected for 5 minutes. The reaction solution was red.Further 20 g of p-tert-butoxystyrene was added. With stirring,polymerization reaction was effected for 30 minutes. Polymerization wasstopped by adding 0.1 mol of methanol to the reaction solution.

For purifying the polymer, the reaction mixture was poured into methanolwhereupon the polymer precipitated. Separation and drying yielded 44 gof a white polymer which was tri-branched poly(p-tert-butoxystyrene).

For producing tri-branched poly(p-hydroxystyrene), 44 g of the abovetri-branched poly(p-tert-butoxystyrene) was dissolved in 400 ml ofacetone. A minor amount of conc. hydrochloric acid was added to thesolution at 60° C., which was stirred for 7 hours. The reaction solutionwas poured into water whereupon the polymer precipitated. Washing anddrying yielded 25 g of a white polymer. Since a peak attributable totert-butyl group was not found in GPC and proton-NMR analysis, thispolymer was confirmed to be tri-branched poly(p-hydroxystyrene) having anarrow molecular weight distribution.

The polymer had a weight average molecular weight (Mw) of 8,500 asanalyzed by GPC and calculated on a polystyrene basis and a dispersity(Mw/Mn) of 1.10.

Synthesis Example 5

Synthesis of Tri-Branchedpoly(p-(1-benzyloxypropyl)-oxystyrene/p-hydroxystyrene)

On the tri-branched poly(p-hydroxystyrene) synthesized in SynthesisExample 4, 1-benzyloxypropyl groups were partially substituted as inSynthesis Example 3.

Synthesis Example 6

Synthesis of Nona-Branched poly(p-hydroxystyrene)

A 2-liter flask was charged with 1000 ml of tetrahydrofuran as a solventand 0.06 mol of sec-butyl lithium as an initiator. To the solution at−78° C. was added 60 g of p-tert-butoxystyrene. With stirring,polymerization reaction was effected for 30 minutes. The reactionsolution turned red. For producing a tri-branched polymer, 0.03 mol ofp-chloromethylstyrene was added to the reaction solution whereuponreaction was effected for 5 minutes. Then 30 g of p-tert-butoxystyrenewas added to the reaction solution, which was stirred for 30 minutes forpolymerization. The reaction solution was red. For producingpenta-branched polymer, 0.015 mol of p-chloromethylstyrene was added tothe reaction solution whereupon reaction was effected for 5 minutes.Then 15 g of p-tert-butoxystyrene was added to the reaction solution,which was stirred for 30 minutes for polymerization. The reactionsolution was red. Finally for producing nona-branched polymer, 0.0075mol of p-chloromethylstyrene was added to the reaction solutionwhereupon reaction was effected for 5 minutes. Then 7.5 g ofp-tert-butoxystyrene was added to the reaction solution, which wasstirred for 30 minutes for polymerization. The reaction solution wasred. Polymerization was stopped by adding 0.1 mol of carbon dioxide gasto the reaction solution.

For purifying the polymer, the reaction mixture was poured into methanolwhereupon the polymer precipitated. Separation and drying yielded 99 gof a white polymer which was nona-branched poly(p-tert-butoxystyrene).

For converting to nona-branched poly(p-hydroxy-styrene), 99 g of theabove nona-branched poly(p-tert-butoxystyrene) was dissolved in 1000 mlof acetone. A minor amount of conc. hydrochloric acid was added to thesolution at 60° C., which was stirred for 7 hours. The reaction solutionwas poured into water whereupon the polymer precipitated. Washing anddrying yielded 66 g of a white polymer. Since a peak attributable totert-butyl group was not found on GPC and proton-NMR analysis, thispolymer was confirmed to be nona-branched poly(p-hydroxystyrene) havinga narrow molecular weight distribution.

The polymer had a weight average molecular weight (Mw) of 11,000 asanalyzed by GPC and calculated on a polystyrene basis and a dispersity(Mw/Mn) of 1.25.

Synthesis Example 7

Synthesis of Nona-Branchedpoly(p-(1-benzyloxypropyl)-oxystyrene/p-hydroxystyrene)

On the nona-branched poly(p-hydroxystyrene) synthesized in SynthesisExample 6, 1-benzyloxypropyl groups were partially substituted as inSynthesis Example 3.

Examples & Comparative Examples

Resist compositions were prepared according to the formulation shown inTables 1 to 3. The components listed in Tables 1 to 3 have the followingmeaning.

Polymer A: poly(p-hydroxystyrene) in which hydroxyl groups are protectedwith 23 mol % of 1-benzyloxypropyl groups, having a weight averagemolecular weight of 11,000.

Polymer B: poly(p-hydroxystyrene) in which hydroxyl groups are protectedwith 10 mol % of 1-benzyloxypropyl groups and 10 mol % oftert-butoxycarbonyl groups, having a weight average molecular weight of11,000.

Polymer C: nano-branched poly(p-hydroxystyrene) in which hydroxyl groupsare protected with 15 mol % of 1-benzyloxypropyl groups and 5 mol % oftert-butoxycarbonyl groups, having a weight average molecular weight of14,000.

Polymer D: poly(p-hydroxystyrene) in which hydroxyl groups are protectedwith 20 mol % of 1-benzyloxypropyl groups and crosslinked with 1 mol %of 1,2-propane diol divinyl ether, having a weight average molecularweight of 13,000.

Polymer E: tri-branched poly(p-hydroxystyrene) in which hydroxyl groupsare protected with 20 mol % of 1-benzyloxypropyl groups, having a weightaverage molecular weight of 11,000.

Polymer F: poly(p-hydroxystyrene) in which hydroxyl groups are protectedwith 22 mol % of 1-phenethyloxypropyl groups, having a weight averagemolecular weight of 12,000.

Polymer G: poly(p-hydroxystyrene) in which hydroxyl groups are protectedwith 20 mol % of 1-phenethyloxypropyl groups and crosslinked with 1 mol% of 1,4-butane diol divinyl ether, having a weight average molecularweight of 13,000.

Polymer H: p-hydroxystyrene/1-ethylcyclopentyl methacrylate copolymerhaving a compositional ratio (molar ratio) of 90:10, hydroxyl groups inthe p-hydroxystyrene being protected with 15 mol % of 1-benzyloxypropylgroups, the copolymer having a weight average molecular weight of12,000.

Polymer I: p-hydroxystyrene/tert-butyl acrylate copolymer having acompositional ratio (molar ratio) of 80:20, hydroxyl groups in thep-hydroxystyrene being protected with 10 mol % of 1-benzyloxypropylgroups, the copolymer having a weight average molecular weight of12,000.

Polymer J: the same as Polymer I further containing 5% by weight ofstyrene and having a weight average molecular weight of 12,000.

Polymer K: p-hydroxystyrene/1-ethylcyclopentyl methacrylate copolymerhaving a compositional ratio (molar ratio) of 90:10, hydroxyl groups inthe p-hydroxystyrene being protected with 10 mol % of 1-benzyloxypropylgroups and crosslinked with 2 mol % of 1,4-butane diol divinyl ether,the copolymer having a weight average molecular weight of 13,000.

Polymer L: poly(p-hydroxystyrene) in which hydroxyl groups are protectedwith 25 mol % of 1-ethoxypropyl groups and crosslinked with 3 mol % of1,2-propane diol divinyl ether, having a weight average molecular weightof 13,000.

Polymer M: poly(p-hydroxystyrene) in which hydroxyl groups are protectedwith 15 mol % of 1-ethoxyethyl groups and 15 mol % oftert-butoxycarbonyl groups, having a weight average molecular weight of12,000.

Polymer N: p-hydroxystyrene/1-ethylcyclopentyl methacrylate copolymerhaving a compositional ratio (molar ratio) of 70:30 and a weight averagemolecular weight of 11,000.

PAG1: triphenylsulfonium 4-toluenesulfonate

PAG2: (4-butoxyphenyl)diphenylsulfonium 10-camphorsulfonate

PAG3: bis(4-butylphenyl)iodonium 10-camphorsulfonate

PAG4: triphenylsulfonium 4-(4-toluenesulfonyloxy)benzene-sulfonate

PAG5: tris(4-butoxyphenyl)sulfonium nonafluorobutane-sulfonate

PAG6: N-(10-camphorsulfonyl)oxy-1,9-naphthalenedicarboxylic acid imide

PAG7: bis(cyclohexylsulfonyl)diazomethane

PAG8: bis(tert-butylsulfonyl)diazomethane

PAG9: bis(2,4-dimethylphenylsulfonyl)diazomethane

Basic compound A: triethanolamine

Basic compound B: tris(2-ethoxyethyl)amine

Organic acid derivative A: 4,4-bis(4′-hydroxyphenyl)valeric acid

Organic acid derivative B: salicylic acid

Surfactant A: FC-430 (Sumitomo 3M K.K.)

Surfactant B: Surflon S-381 (Asahi Glass K.K.)

UV absorber: 9,10-dimethylanthracene

Solvent A: propylene glycol methyl ether acetate

Solvent B: ethyl lactate

Each resist solution was passed through a 0.2 μm Teflon filter and spincoated onto a silicon wafer which had been coated with an organicantireflection film (DUV-44 by Brewer Science) to a thickness of 800 Å.The coated silicon wafer was baked on a hot plate at 100° C. for 90seconds. The thickness of the resist film was set at 0.6 μm.

The resist film was exposed through the patterned mask using an excimerlaser stepper (NSR-S202A, from Nikon Corporation; NA=0.6 2/3 annular)baked at 110° C. for 90 seconds (PEB) and developed with a 2.38 wt %solution of tetramethylammonium hydroxide in water, thereby giving apositive pattern (Examples 1-24 and Comparative Examples 1-3).

The resist patterns obtained were evaluated as described below.

Resist Pattern Evaluation

The optimal exposure dose (sensitivity, Eop) was defined as the dosewhich provides a 1:1 resolution at the top and bottom of a 0.15 μmline-and-space pattern. The resolution of the resist under evaluationwas defined as the minimum line width of the lines and spaces thatseparated at this dose. The shape in cross section of the resolvedresist pattern was examined under a scanning electron microscope.

The depth of focus (DOF) was determined by offsetting the focal pointand judging the resist to be passed when the resist pattern shape waskept rectangular and the resist pattern film thickness was kept above80% of that at accurate focusing.

The PED stability of a resist was evaluated by effecting post-exposurebake (PEB) after 24 hours of holding from exposure at the optimum doseand determining a variation in line width.

The results of resist pattern evaluation are shown in Table 4.

Other Evaluation

The solubility of resist material in a solvent mixture was examined byvisual observation and in terms of clogging upon filtration.

With respect to the applicability of a resist solution, uneven coatingwas visually observed. Additionally, using a film gage Clean Track Mark8 (Tokyo Electron K.K.), the thickness of a resist film on a commonwafer was measured at different positions, based on which a variationfrom the desired coating thickness (0.6 μm) was calculated. Theapplicability was rated “good” when the variation was within 0.5% (thatis, within 0.003 μm), “unacceptable” when the variation was within 1%,and “poor” when the variation was more than 1%.

Storage stability was judged in terms of particle precipitation orsensitivity change during aging. After the resist solution was aged for100 days at the longest, the number of particles of greater than 0.3 μmper ml of the resist solution was counted by means of a particle counterKL-20A (Rion K.K.), and the particle precipitation was determined “good”when the number of particles is not more than 5. Also, the sensitivitychange was rated “good” when a change with time of sensitivity (Eop) waswithin 5% from that immediately after preparation, and “poor” when thechange is more than 5%.

Defect appearing on the developed pattern was observed under a scanningelectron microscope (TDSEM) model S-7280H (Hitachi K.K.). The resistfilm was rated “good” when the number of foreign particles was up to 10per 100 μm², “unacceptable” when from 11 to 15, and “poor” when morethan 15.

Defect left after resist stripping was examined using a surface scannerSurf-Scan 6220 (Tencol Instruments). A resist-coated 8-inch wafer wassubjected to entire exposure rather than patterned exposure, processedin a conventional manner, and developed with a 2.38% TMAH solutionbefore the resist film was peeled off (only the resist film in theexposed area was peeled). After the resist film was peeled, the waferwas examined and rated “good” when the number of foreign particles ofgreater than 0.20 μm was up to 100, “unacceptable” when from 101 to 150,and “poor” when more than 150.

The results are shown in Table 5.

TABLE 1 Composition (pbw) E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 E11 E12 PolymerA 80 40 Polymer B 80 Polymer C 80 Polymer D 80 Polymer E 80 Polymer F 80Polymer G 80 Polymer H 80 40 Polymer I 80 Polymer J 40 Polymer K 80Polymer L 40 Polymer M Polymer N PAG1 2 PAG2 2 2 2 2 2 PAG3 2 1 2 2 PAG42 2 2 PAG5 1 1 PAG6 2 2 PAG7 2 2 PAG8 1 PAG9 1.5 1 1 1 Dissolutioninhibitor Basic compound A 0.3 0.3 0.3 0.3 0.3 0.15 0.3 0.3 Basiccompound B 0.3 0.15 0.3 0.3 0.3 Organic acid 1 1 1 1 1 1 1 derivative AOrganic acid 1 1 1 1 1 derivative B Surfactant A 0.25 0.25 0.25 0.250.25 0.25 Surfactant B 0.25 0.25 0.25 0.25 0.25 0.25 UV absorber SolventA 385 280 385 280 280 280 280 280 280 280 280 280 Solvent B 105 105 105105 105 105 105 105 105 105

TABLE 2 Composition (pbw) E13 E14 E15 E16 E17 E18 E19 E20 E21 E22 E23E24 Polymer A 40 40 60 Polymer B 20 75 Polymer C 20 40 80 Polymer D 4040 60 40 Polymer E 40 Polymer F Polymer G 40 40 Polymer H 60 40 PolymerI 20 Polymer J Polymer K 40 60 Polymer L 20 Polymer M 20 Polymer N PAG12 20 PAG2 2 2 2 PAG3 2 1 2 2 2 1 PAG4 2 2 2 PAG5 1 1 1 PAG6 2 2 PAG7 2.51.5 PAG8 0.5 PAG9 1.5 1 1 1 Dissolution 5 inhibitor Basic compound A0.15 0.3 0.3 0.3 Basic compound B 0.15 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3Organic acid 1 1 1 1 1 1 derivative A Organic acid 1 1 1 1 1 1 1derivative B Surfactant A 0.25 0.25 0.25 0.25 0.25 0.25 0.25 SurfactantB 0.25 0.25 0.25 0.25 0.25 UV absorber 0.5 Solvent A 385 280 280 280 385280 280 280 280 280 280 280 Solvent B 105 105 105 105 105 105 105 105105 105

TABLE 3 Composition (pbw) CE1 CE2 CE3 Polymer L 80 Polymer M 80 PolymerN 80 PAG1 PAG2 PAG3 PAG4 PAG5 PAG6 PAG7 PAG8 2 2 PAG9 2 Dissolutioninhibitor Basic compound A 0.3 Basic compound B 0.3 0.3 Organic acidderivative A 1 1 1 Organic acid derivative B Surfactant A 0.25 0.25Surfactant B 0.25 UV absorber Solvent A 280 385 280 Solvent B 105 105

TABLE 4 DOF for 24 hr PED Sensitivity Resolution Profile 0.15 μm Profiledimensional (mJ/cm²) (μm) shape (μm) shape* stability (nm) E1  26 0.14rectangular 1.0 rectangular −10 E2  30 0.14 rectangular 1.0 rectangular−5 E3  27 0.14 rectangular 1.0 rectangular −8 E4  25 0.14 rectangular0.9 rectangular −8 E5  27 0.14 rectangular 1.0 rectangular −10 E6  300.15 rectangular 1.0 rectangular −6 E7  28 0.14 rectangular 1.0rectangular −8 E8  27 0.14 rectangular 1.0 rectangular −12 E9  32 0.14rectangular 1.0 rectangular −10 E10 30 0.14 rectangular 1.0 rectangular−10 E11 28 0.14 rectangular 1.0 rectangular −8 E12 27 0.14 rectangular1.0 rectangular −10 E13 27 0.14 rectangular 1.0 rectangular −8 E14 260.14 rectangular 1.0 rectangular −10 E15 26 0.14 rectangular 1.0rectangular −10 E16 26 0.15 rectangular 1.0 rectangular −8 E17 28 0.14rectangular 1.0 rectangular −10 E18 27 0.14 rectangular 1.0 rectangular−8 E19 27 0.14 rectangular 1.0 rectangular −10 E20 28 0.14 rectangular1.0 rectangular −10 E21 26 0.14 rectangular 1.0 rectangular −10 E22 280.14 rectangular 1.0 rectangular −10 E23 27 0.14 rectangular 1.0rectangular −8 E24 26 0.14 rectangular 1.0 rectangular −8 somewhat CE123 0.15 rounded head 0.6 rounded head −10 CE2 27 0.15 rounded head 0.6rounded head −8 CE3 27 0.15 forward 0.6 forward −10 tapered tapered *Thepattern shape when the focal point was offset −0.4 μm on the minus sideupon measurement of DOF for the 0.15 μm line-and-space pattern.

TABLE 5 100 day storage Defect after Dissolution Application stabilityDevelopment E1  good good good good E2  good good good good E3  goodgood good good E4  good good good good E5  good good good good E6  goodgood good good E7  good good good good E8  good good good good E9  goodgood good good E10 good good good good E11 good good good good E12 goodgood good good E13 good good good good E14 good good good good E15 goodgood good good E16 good good good good E17 good good good good E18 goodgood good good E19 good good good good E20 good good good good E21 goodgood good good E22 good good good good E23 good good good good E24 goodgood good good CE1 good good <30 days good (sensitivity changed) CE2good unacceptable <30 days unacceptable (sensitivity changed) CE3 goodgood good poor

There have been described chemical amplification type positive resistcompositions comprising a resin having substituents of formula (1). Thecompositions have many advantages including improved resolution,minimized line width variation or shape degradation even on long-termPED, minimized defect left after coating, development and stripping, andimproved pattern profile after development. The compositions areimproved in focal latitude in that the pattern profile maintainsrectangularity and undergoes minimized slimming when the focal point isoffset. The compositions are thus suited for microfabrication by anylithography, especially deep UV lithography.

Japanese Patent Application No. 2000-061350 is incorporated herein byreference.

Although some preferred embodiments have been described, manymodifications and variations may be made thereto in light of the aboveteachings. It is therefore to be understood that the invention may bepracticed otherwise than as specifically described without departingfrom the scope of the appended claims.

What is claimed is:
 1. A chemical amplification, positive resistcomposition comprising (A) a photoacid generator and (B) a resin whichchanges its solubility in an alkali developer under the action of acidand has substituents of the following general formula (1):Ph—(CH₂)_(n)OCH(CH₂CH₃)—  (1) wherein Ph is phenyl and n is 1 or 2, andwherein resin (B) is a branched, alkali-soluble resin comprising unitsof the following formula (2″) wherein some of the hydrogen atoms onphenolic hydroxyl groups are protected with substituents of the formula(1),

wherein R⁴ is hydrogen or methyl, R⁵ is a straight, branched or cyclicalkyl group of 1 to 8 carbon atoms, x is 0 or a positive integer, y is apositive integer, satisfying x+y≦5, ZZ is a divalent organic groupselected from the group consisting of CH₂, CH(OH), CR⁵(OH), C═O, andC(OR⁵)(OH), or a trivalent organic group represented by —C(OH)═, E maybe the same or different and is a positive integer, K is a positiveinteger, satisfying 0.001 □K/(K+E)=0.1, and XX is 1 or
 2. 2. A positiveresist composition of claim 1, wherein the resin (B) further has acidlabile groups.
 3. A positive resist composition of claim 2, wherein theresin (B) further has acid labile groups which are selected from theclass consisting of groups of the following general formulae (4) to (7),tertiary alkyl groups of 4 to 20 carbon atoms, trialkylsilyl groups inwhich each alkyl moiety has 1 to 6 carbon atoms, and oxoalkyl groups of4 to 20 carbon atoms,

wherein R¹⁰ and R¹¹ each are hydrogen or a straight, branched or cyclicalkyl group of 1 to 18 carbon atoms, R¹² is a monovalent hydrocarbongroup of 1 to 18 carbon atoms which may contain a hetero atom, a pair ofR¹⁰ and R¹¹, R¹⁰ and R¹², or R¹¹ and R¹² may form a ring, each of R¹⁰,R¹¹ and R¹² is a straight or branched alkylene group of 1 to 18 carbonatoms when they form a ring, R¹³ is a tertiary alkyl group of 4 to 20carbon atoms, a trialkylsilyl group in which each alkyl moiety has 1 to6 carbon atoms, an oxoalkyl group of 4 to 20 carbon atoms, or a group offormula (4), z is an integer of 0 to 6, R¹⁴ is a straight, branched orcyclic alkyl group of 1 to 8 carbon atoms or a substituted orunsubstituted aryl group of 6 to 20 carbon atoms, h is equal to 0 or 1,and i is equal to 0, 1, 2 or 3, satisfying 2h+i=2 or 3, R¹⁵ is astraight, branched or cyclic alkyl group of 1 to 8 carbon atoms or asubstituted or unsubstituted aryl group of 6 to 20 carbon atoms, R¹⁶ toR²⁵ are independently hydrogen or monovalent hydrocarbon groups of 1 to15 carbon atoms which may contain a hetero atom, R¹⁶ to R²⁵, takentogether, may form a ring, and each of R¹⁶ to R²⁵ represents a divalenthydrocarbon group of 1 to 15 carbon atoms which may contain a heteroatom, when they form a ring, or two of R¹⁶ to R²⁵ which are attached toadjoining carbon atoms may bond together directly to form a double bond.4. A positive resist composition according to claim 3, wherein R¹⁰ andR¹¹ are each H or a straight, branched or cyclic alkyl group of 1-10carbon atoms; R¹² is a monovalent hydrocarbon group of 1-10 carbon atomswhich may contain an oxygen atom; R¹³ is tert-butyl, tert-amyl,1,1-diethylpropyl, 1-methylcyclopentyl, 1-ethylcyclopentyl,1-isopropylcyclopentyl, 1-butylcyclopentyl, 1-methylcyclohexyl,1-ethylcyclohexyl, 1-isopropylcyclohexyl, 1-butylcyclohexyl,1-ethyl-2-cyclo-pentenyl, 1-ethyl-2-cyclohexenyl, 2-methyl-2-adamantyl,trimethylsilyl, triethylsily, dimethyl-tert-butylsilyl, 3-oxocyclohexyl,4-methyl-2-oxooxan-4-yl, or 5-methyl-5-oxooxoran-4-yl; R¹⁴ is methyl,ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl,n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, cyclopentylmethyl,cyclopentylethyl, cyclohexylmethyl and cyclohexylethyl, phenyl,methylphenyl, naphthyl, anthryl, phenanthryl, or pyrenyl; R¹⁵ is methyl,ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl,n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, cyclopentylmethyl,cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, phenyl,methylphenyl, naphthyl, anthryl, phenanthryl, or pyrenyl; and R¹⁶-R²⁵are each independently, methyl, ethyl, propyl, isopropyl, n-butyl,sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, n-octyl, n-nonyl,n-decyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl,cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, which in each caseis unsubstituted or substituted by hydroxyl, alkoxy, carboxy,alkoxycarbonyl, oxo, amino, alkylamino, cyano, mercapto, alkylthio, orsulfo groups.
 5. A positive resist composition according to claim 2,wherein the total content of substituents of formula (1) and other acidlabile groups is 1-80 mol % based on the phenolic hydroxy groups and/orcarboxyl groups in the original alkali-soluble resin.
 6. A positiveresist composition according to claim 1, wherein resin (B) has a weightaverage molecular weight of 3,000-100,000.
 7. A positive resistcomposition according to claim 1, wherein the polydispersity index ofresin (B) is up to 3.5.
 8. A positive resist composition according toclaim 1, wherein the polydispersity index of resin (B) is up to 1.5. 9.A positive resist composition according to claim 1, wherein in resin (B)the proportion of substituents of formula (1) in the resin is 1-40 mol %based on the phenolic hydroxy groups and/or carboxyl groups in thestarting alkali-soluble resin.
 10. A positive resist compositionaccording to claim 1, wherein in resin (B) the proportion ofsubstituents of formula (1) in the resin is 5-30 mol % based on thephenolic hydroxy groups and/or carboxyl groups in the startingalkali-soluble resin.
 11. A positive resist composition according toclaim 1, wherein in resin (B) the proportion of substituents of formula(1) in the resin is 10-25 mol % based on the phenolic hydroxy groupsand/or carboxyl groups in the starting alkali-soluble resin.
 12. Apositive resist composition according to claim 1, wherein in resin (B)the hydrogen atoms on phenolic hydroxy groups are replaced bysubstituents of formula (1) in a proportion of more than 1 mol % to 40mol %, based on the total hydrogen atoms of phenolic hydroxy groups, andthe polymer has a weight average molecular weight of 3,000-100,000. 13.A positive resist composition according to claim 1, wherein R⁵ ismethyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl,cyclohexyl or cyclopentyl.
 14. A positive resist according to claim 1,wherein Ris H.
 15. A positive resist composition according to claim 1,further comprising an organic solvent.
 16. A positive resist compositionaccording to claim 15, further comprising (C) a resin which changes itssolubility in an alkali developer under the action of the acid and isfree of substituents of formula (1).
 17. A positive resist compositionaccording to claim 15, wherein said composition further comprises (D) abasic compound.
 18. A positive resist composition according to claim 15,wherein said composition further comprises (E) an organic acidderivative.
 19. A positive resist composition according to claim 15,wherein said composition further comprises (F) a compound with amolecular weight of up to 3,000 which changes its solubility in analkali developer under the action of acid.